Electrophilic Addition Reaction - II

E
C C + E Nu C C
Nu
ELECTROPHILIC ADDITION
REACTIONS: ALKENES & ALKYNES
THE STEREOCHEMISTRY OF
ADDITION REACTIONS
P. Shanika
pshanika@unam.na
W264
Ext: 4590
Type of Organic Reactions
Additions
Substitutions
Eliminations
Rearrangements
Others:
o Pericyclic,
o Polymerization,
o Redox reactions.
ELECTROPHILIC ADDITION REACTIONS_P.SHANIKA 2

Alkenes & Alkynes
Addition reactions:
Halogenation (addition of halogens)
Halohydrin formation – or halo alcohol
Hydrohalogenation
Hydration
Addition of sulphuric acid
Hydrogenation

Stability of Alkenes
The greater the number of attached alkyl groups
(i.e., the more highly substituted the carbon atoms of
the double bond), the greater is the alkene’s stability.

Exercise
Consider the two alkenes 2-methyl-1-pentene
and 2-methyl-2-pentene and decide which is
the most stable.

Addition Reactions of Alkenes
E
C C + E Nu C C
Nu
Double bond is composed of a  bond &  bond; but  bond is
weaker than  bond and therefore more easily broken.
Double bond supplies pi electrons and is therefore electron rich
(nucleophile)

Electrophiles
(“electron loving”)
An electrophile has
a positive charge,
a partial positive charge, (polarizable)
or an incomplete octet (empty orbital)
or a heterolytically breakable bond (to a leaving group)
Electrophiles:
Organic reagents
Electrophile, E+ (= electron acceptors) are electron poor reagents;
they seek electrons
Given the same electrophilic atom, a greater degree of positive
charge gives a stronger electrophile

Electrophile: Examples
Note: some electrophiles are neutral and some have a full or

partially positive charge
Nucleophiles
Electron-rich atoms or molecules
A nucleophile has
• a negative charge
• loosely held electrons e.g.,
• a lone pair e.g., :NH3
• or  electrons CH2=CH2, not  electrons.
Nucleophiles:
Organic reagents
Nucleophile, Nu:- or Nu: (= electron donors) are electron rich;
form bonds by donating electrons to the electrophile
For two nucleophiles with the same nucleophilic atom, a negative
charge makes the atom more reactive (or the stronger base is the
stronger nucleophile -given the same nucleophilic atom):

Nucleophile: Examples
Note: some nucleophiles are neutral and some have a full or

partially negative charge
How To Understand Additions
to Alkenes
 E–Nu added across the double bond
E
C C + E Nu C C
Nu
-bond -bond 2 -bonds
Bonds broken Bonds formed

 Since  bonds are formed from the
overlapping of p orbitals,  electron clouds
are above and below the plane of the
double bond
 electron clouds
C C

Reactions of Alkenes
-bond lobes represent
areas of high electron
density; it can therefore
attack a electron poor
molecule (E+)

 In an electrophilic addition, the 
electrons seek an electrophile,
breaking the  bond, forming a  bond
and leaving a positive charge on the
vacant p orbital on the adjacent
carbon. Addition of a nucleophile to
form a  bond provides an addition
product.

 Electrophilic:
● electron seeking
● C=C and C≡C  bonds are
particularly susceptible to
electrophilic reagents
(electrophiles)

 Common electrophiles:
 Bronsted-Lowry acids (proton donors)
 Lewis acids (BH3, BF3, and AℓCℓ3
 Neutral compounds (Br2)
 Metal ions with vacant orbitals (Ag+,
Hg2+, & Pt2+)
● H+, X+ (X = Cℓ, Br, I), Hg2+, etc.


Outline
Addition of Hydrogen halides, HX (Hydrohalogenation)
◦ Markovnikov’s Rule
◦ Anti-Markovnikov’s Rule
Addition of Water, H2O (Hydration)
◦ acid-catalyzed addition of water
◦ oxymercuration–demercuration
◦ hydroboration oxidation
Addition of Alcohols, ROH
◦ acid-catalyzed addition of alcohol
◦ alkoxymercuration–demercuration
Addition of Halogens, X2, X = Cℓ, Br (Halogenation)
Formation of Halohydrins,
Addition of Hydrogen, H2 (Hydrogenation / Reduction)

Addition of Hydrogen halides, HX
•Addition of hydrogen halides, HX (with X = Cℓ, Br, I) to alkenes 
Hydrohalogenation
Reactivity: HI > HBr > HCℓ > HF
Example:

 
E Nu
C C
Nu E
C C

E
C C + E Nu C C
Nu

• carbon atoms of a double bond are both trigonal planar,
• X and Y added on the same side or from opposite sides.

Hydrohalogenation Mechanism
Which process looks more favorable?

Markovnikov and anti-Markovnikov

Electrophilic Addition of Hydrogen Halides to
Alkenes: Mechanism & Markovnikov’s Rule
 Mechanism

Symmetrical Alkenes: Mechanism & Markovnikov’s Rule
H H E E
E Nu same
C C H C C H as H C C H
H H H H H H
Nu
E Nu Nu E
same
H C C H as H C C H
H H H H
Asymmetric Alkenes: Mechanism & Markovnikov’s Rule
H3C H E E
E Nu
C C CH3 C C H or CH3 C C H
H H H H H H
Nu Nu
E Nu different Nu E
CH3 C C H from CH3 C C H
H H H H

Markovnikov’s Rule
● Electrophilic addition of an electrophile across an
asymmetrical alkene,
● The more highly substituted and more stabilized
carbocation is formed

Symmetrical versus asymmetrical alkenes
CH2=CH2 CH3CH=CH2
CH3CH=CHCH3 CH3CH2CH=CHCH3

Note: carbocation stability  3 > 2 > 1

o o o

 Addition of Hydrogen Halides
● Addition of HCℓ, HBr and HI across a C=C
bond
● H is the electrophile
+
  Br
  slow Br
+ H Br
r.d.s fast
Br
NO

Theoretical Explanation ofMarkovnikov’s Rule
 
H3C H
H X
C C or
step 1
H H (slow
r.d.s.) 2o carbocation 1o carbocation
(more stable) (less stable)
 Markovnikov’s rule is to say that in the addition of HX to an

alkene, the hydrogen atom adds to the carbon atom of
the double bond that already has the greater number
of hydrogen atoms

Propene + HBr
H H
Br
☓ (1o cation) fast

(minor)
Br
H Br
slow
(r.d.s.)
H H
Br
(2o cation) fast

Br
(major)
 Examples
H H
H H Cl H H H
H Cl H H
(1) +
H
H H Cl
H
H
(95 : 5)
H Br
H Br
(2) +
Br H
(98 : 2)
General Statement of
 In the ionic addition of an asymmetrical
reagent to a double bond, the positive
portion of the added reagent attaches
itself to a carbon atom of the double
bond so as to yield the more stable
carbocation as an intermediate

 Examples OH
OH
Cl Cl
Hypochlorous acid
  more stable (major)
Cl OH 3o cation
(1)

 Examples
Cl
I I
Iodine monochloride Cl
more stable (major)
3o cation

Regioselective Reactions
 reaction potentially yield two or more constitutional isomers but

actually produces only one (or a predominance of one), the
reaction is said to be regioselective
Cl H
H Cl
+
H Cl
(major) (minor)
regioisomers
Regioselectivity: 95 : 5
An Exception to Markovnikov’s
Rule
 When alkenes are treated with HBr in the

presence of peroxides.
 This anti-Markovnikov addition does not take
place with HI, HCℓ, and HF, even when
peroxides are present.
 Via a radical mechanism
Free Radical Initiation
Peroxide O-O bond breaks easily to form free radicals (alkoxy radical=RO.)
heat
R O O R R O + O R
• Hydrogen is abstracted from HBr.
R O + H Br R O H + Br
Electrophile

Anti-Markovnikov ??
CH3
CH3 C CH CH3
CH3 Br
CH3 C CH CH3 + Br CH3
X CH3 C CH CH3
Br
Tertiary radical is more stable, so that intermediate forms faster

Markovnikov and Anti-Markovnikov addition
H
H-Br Br H H Br
C H +
H3CH2C C H3CH2C C C H H3CH2C C C H
H H H H H
Polar mechanism none of this
(Markovnikov addition)
H
H-Br Br H H Br
C H +
H3CH2C C H3CH2C C C H H3CH2C C C H
H peroxides H H H H
(RO-OR)
none of this
Radical mechanism
(Anti-Markovnikov addition)

Which of the following compounds will react most rapidly with HCℓ?
1
2
3
4
5

Which of the following compounds will react most rapidly with HCℓ?
1
2
3
4
5
Both 1 and 2 will form the same stable
tertiary carbocation. However, alkene 1 is
less stable than 2 and will react faster.

Rank the following compounds in order from most stable to least
stable.
1>2>3>4
1>2>4>3
4>1>2>3
4>3>2>1
2>4>1>3

Rank the following compounds in order from most stable to least
stable.
1>2>3>4
1>2>4>3
4>1>2>3
4>3>2>1
4 is the most highly substituted; trans 2>4>1>3
is more stable than cis; cyclopentene
is similar to 2 but also has some
ring strain.

Stereochemistry of the Ionic
Addition to an Alkene
X
attack from top X
H C CH3
Bu
(S)-2-Halohexane
racemate
H H
H X H (50%)
C C C CH2 H
Bu
Bu H
achiral
trigonal planar H
carbocation Bu C CH3
X X
attack from bottom (R)-2-Halohexane
(50%)
Addition of Hydrogen halides
Constitutional
Asymmetrical alkene isomers
Carbocation intermediates (2) have equal stabilities, therefore

approx. equal amounts of the two alkyl halide will be formed.
Exercise
• What would be the major product obtained from the addition of
HBr to each of the following compounds :
(a)CH3CH2CH=CH2 (b) CH3CH=CHCH3
(c) (d)
(e) (f)

Outline
Addition of Hydrogen halides, HX (Hydrohalogenation)
Addition of Water, H2O (Hydration)
Addition of Alcohols, ROH
Addition of Halogens, X2, X = Cℓ, Br (Halogenation)
Formation of Halohydrins,
Addition of Hydrogen, H2 (Hydrogenation / Reduction)
Addition of water (H2O)
Water is too weak an acid to transfer the proton to the alkene:
CH3CH=CH2 + H2O  No Reaction
The hydration of alkenes and alkynes requires the addition of a strong acid catalyst.
◦ Usually H2SO4
◦ Leads to formation of the hydronium ion

Acid catalyzed addition of water follows Markovnikov’s rule
Product of reaction = alcohol
Example:
H+
CH3CH=CH2 + H2O CH3CHCH3
propene
2-propanol

H
Mechanism
H O H H2O
H H
slow fast
(step 1) (step 2)
O
more stable H H
3o cation
fast H2O
(step 3)
H H
H O H +
OH

Rearrangements
 Rearrangement can occur with certain carbocations
H2O
H
H2SO4
NOT 1,2-alkyl shift

OH
H2O

Rearrangements Are Possible
Methyl Shift:
CH3 CH3 CH3
CH3 C CH CH3 CH3 C CH CH3 CH3 C CH CH3
CH3 CH3 OH CH3
2o, less stable 3o, more stable 2,3-dimethyl-2-butanol

(major product)
A methyl shift after protonation will produce the more stable tertiary carbocation.
ELECTROPHILIC ADDITION REACTIONS_P.SHANIKA 59 59

Mechanism for acid-catalyzed addition of water:
carbocation
Step 1: addition of electrophile (H+) & formation of carbocation intermediate

Step 2: carbocation intermediate react with molecule of water to form oxonium
Step 3: (deprotonation) proton is transferred to a molecule of water to yield
product (alcohol)
• Mechanism for acid-catalyzed addition of water:

Exercise
Write a mechanism for the acid-catalyzed addition of water to:

(i) 2-butene
(ii) 3-hexane
(iii) 3,3-Dimethylbut-1-ene

Oxymercuration-Demercuration Reaction
Reagent is mercury(II) acetate, Hg(OAc)2

+Hg(OAc) is the electrophile that adds to the 𝜋 bond.
The intermediate is a three-membered ring called the mercurinium
ion.
Follows Markovnikov’s rule.
Milder conditions than direct hydration.
No rearrangements or polymerization.

Oxymercuration
Reagent is mercury(II) acetate which dissociates
slightly to form +Hg(OAc).
+Hg(OAc) is the electrophile that attacks the pi bond.
O O O O
_ +
CH3 C O Hg O C CH3 CH3 C O Hg O C CH3

Oxymercuration
The intermediate is a cyclic mercurinium ion, a three-membered ring with
a positive charge.
OAc
+
Hg
+
C C Hg(OAc) C C

Oxymercuration
Water approaches the mercurinium ion from the
side opposite the ring (anti addition).
Water adds to the more substituted carbon to form
the Markovnikov product.
OAc OAc OAc
+ Hg
Hg Hg
C C C C C C
+
H O O
H2O H H
H2O

Demercuration
Sodium borohydride, a reducing agent, replaces the mercury with
hydrogen.
OAc
Hg H
_
4 C C + NaBH4 + 4 OH 4 C C + NaB(OH)4
_
O O
+ 4 Hg + 4 OAc
H H

Oxymercuration–Demercuration of
3,3-Dimethylbut-1-ene
The reaction does not suffer from rearrangements because

there is no carbocation intermediate.
Chapter
ELECTROPHILIC ADDITION 8
REACTIONS_P.SHANIKA 68 68
Stereochemistry of the Mercurinium Ion
Opening
Water adds to the more substituted carbon to form the

Markovnikov product.
Water approaches the mercurinium ion from the side opposite the
ring (anti addition).
Chapter
Demercuration Reaction
In the demercuration reaction, a hydride furnished by the sodium borohydride

(NaBH4) reduces the acetoxymercury group and replaces it with hydrogen.
The overall reaction gives the Markovnikov product with the hydroxy group on the
most substituted carbon.
Chapter
Mechanism of Oxymercuration
 Does not undergo a “free carbocation”
 H2O attacks the carbon of the bridged Hg ion that is
better able to bear the partial +ve charge

HgOAc
AcO + 
H2O
HgOAc
HO H2O

Oxymercuration-Demercuration Reaction Mechanism
Step 1
Hg(OAc)2 ⇌ +HgOAc + OAc−
Mercuric acetate dissociates to form

+HgOAc cation and an acetate anion.

Step 2

Step 3 & 4

The Oxymercuration-
Demercuration Reaction
• A means of avoiding rearrangements
Markovnikov Hydration

Rearrangements Seldom Occur in
Oxymercuration–Demercuration
 Recall: acid-catalyzed hydration of some

alkenes leads to rearrangement products
 Driving force for rearrangement:
Formation of a more stable 3° cation
e.g.
OH
H2O
H
H2SO4

Exercise
Write the structure of the appropriate alkene
and specify the reagents needed for the
synthesis of the following alcohols by
oxymercuration-demercuration:

Alcohols from Alkenes Hydroboration–Oxidation:
Anti-Markovnikov Syn Hydration
"BH3"
C C C C
H BH2
 Addition of H–BH2 (borane) across a C=C

bond

BH3 (Borane) is an Electrophile
Like a methyl
cation, it has
an empty p
orbital that
can accept
electrons.

 BH3 exists as dimer B2H6 (diborane) or
complex with coordinative solvent
H H
H B B H
H H
H H Me
H B O H B S
H H Me
(BH3-THF) (BH3-DMS)
Borane in tertrahydrofuran and in dimethyl sulphide
Hydroboration–Oxidation

Hydroboration of Alkenes
Borane adds to alkenes with anti-

Markovnikov orientation to form
alkylboranes, which after oxidation give anti-
Markovnikov alcohols.

syn addition
Anti-Markovnikov addition
of “H” & “OH”

Compare with oxymercuration-demercuration
OH H
Hg(OAc)2
THF-H2O
H3C H CH3 Hg(OAc)
NaBH4
Markovnikov addition OH H
of “H” & “OH” anti addition
CH3 H
Mechanism of Hydroboration
Borane adds to the double bond in a single step, with boron

adding to the less substituted carbon and hydrogen adding to the
more highly substituted carbon.
This orientation places the partial positive charge in the transition
state on the more highly substituted carbon atom.
Mechanism of Hydroboration
The hydroboration step adds the hydrogen and the boron to

the same side of the double bond (syn addition).
Oxidation of the alkyl borane with basic hydrogen peroxide
(H2O2 in a base), produces the alcohol.
Orientation is anti-Markovnikov.
Chapter
Mechanism for Hydroboration

Mechanism for the Oxidation
Reaction

Hydroboration Examples
The use of (1) and (2) above and below the reaction
arrow indicates individual steps in a two-step reaction!
The Electrophile Adds to the sp2 Carbon
Bonded to the Most Hydrogens
The reagents are numbered because the second set

of reagents is not added until the first reaction is over.

Summary: Addition of water
(HOH)-unsymmetrical alkenes
◦ Acid catalyzed addition of water gives
◦ Markovnikov product;
◦ Carbocation intermediate
◦ Rearrangements
◦ Syn and anti addition
◦ Oxymercuration-demercuration reaction
◦ Markovnikov product;
◦ no carbocation intermediate;
◦ Anti addition
◦ Hydroboration-oxidation reaction
◦ Anti-Markovnikov product;
◦ Syn addition

Summary of Alkene Hydration
Methods
Summary of Methods for Converting Alkene to Alcohol
Occurrence of
Reaction Regiochemistry Stereochemistry Rearrangements
Acid-catalyzed Markovnikov Not controlled Frequent
hydration addition
Oxymercuration- Markovnikov Not controlled Seldom

demercuration addition
Hydroboration- Anti-Markovnikov Stereospecific: Seldom

oxidation addition syn addition of
–H and –OH
 Examples via H
1,2-hydride
H shift
H OH Markovnikov addition of H2O

H with rearrangement
H2O
Markovnikov, anti addition of

H2O without rearrangement
anti-Markovnikov,
syn addition of H2O

Exercise & Solution
• Show how you would convert
1-methylcyclopentene to
2-methylcyclopentanol.
Solution:
Working backward, use hydroboration–oxidation to
form 2-methyl cyclopentanol from 1-
methylcyclopentene.

Outline
Acid-Catalyzed Addition of an
Alcohol
• Addition of alcohol requires acid catalyst (H+ or

H3O+)
• Product of reaction = ether (Markovnikov)

Acid-Catalyzed Addition of an
Alcohol
 Mechanism for the acid-catalyzed addition of an
alcohol is essentially the same as the mechanism for
the acid-catalyzed addition of water.
 Nucleophile in this case is ROH instead of HOH.

Mechanism for the
Acid-Catalyzed Addition of an Alcohol
Rearrangement of carbocation intermediate is possible!

Mechanism for the
Acid-Catalyzed Addition of an Alcohol
Another mechanism:
Rearrangement of carbocation intermediate is possible!

Alkoxymercuration–Demercuration
Compare with oxymercuration-demercuration.
If the nucleophile is an alcohol (ROH), instead of water an ether is
produced.(Markonikov)

Exercise
• Show the intermediates and products that
result from alkoxymercuration–
demercuration of 1-methylcyclopentene,
using methanol as the solvent.
• Draw the product formed in each reaction.
H2 O
H2SO4
CH3CH2CH2CH2CH=CH2
1. BH3
2. H2O2, HO-
Outline
Addition of Halogen, X2
Cℓ2, Br2, and sometimes I2 add to a double bond to form a vicinal dihalide.
This is an anti addition of halides.
Examples:
Cl2
Br2

Addition of Halogen, X2
Mechanism:
Step 1: Bromine molecule becomes polarised; bromine bond breaks heterolytically;

formation of the cyclic bromonium cation and bromide anion.
Step 2: Back-side nucleophilic attack & opening of the three membered ring give
product
Note: This back-side attack assures anti stereochemistry of addition,
i.e. the two bromine atoms add to opposite sides of the double bond
= anti addition ELECTROPHILIC ADDITION REACTIONS_P.SHANIKA 104
Addition of Br2 or Cℓ2

The Product is a Vicinal Dihalide

No Carbocation Rearrangements

Alkenes Do Not Add I2

Bromonium Ion Formation
The same reaction with chlorine

affords a chloronium ion:
Because of the structural symmetry of
the cyclohexyl bromonium ion, a
racemic mixture of the trans dibromo
product is formed
Bromine Test for Unsaturation
The bromination reaction is used
as a diagnostic test for alkenes and
alkynes
Add Br2 in CCℓ4 (dark, red-brown
color) to an alkene.
The color quickly disappears as the
bromine adds to the double bond
(left-side test tube).
If there is no double bond present,
the brown color will remain (right
side).
“Decolorizing bromine” is the
chemical test for the presence of a
Outline
Formation of Halohydrins
Halohydrins are a class of compounds containing halogen and OH
functional groups.
If the halogen and OH groups are on adjacent carbon atoms, the
compound is called a vicinal halohydrin:

If a halogen is added in the presence of water as solvent, a halohydrin is

formed.
Water is the nucleophile.
This is a Markovnikov addition: The bromide (electrophile) will add to the less
substituted carbon.
Chapter
Mechanism of Halohydrin Formation
Chapter
Mechanism for Halohydrin Formation

Stereochemistry of Halohydrins
Because the mechanism involves a

halonium ion, the stereochemistry of
addition is anti, as in halogenation.

Orientation of Halohydrin
Formation
The more substituted carbon of the chloronium ion

bears more positive charge than the less substituted
carbon.
Attack by water occurs on the more substituted
carbon to give the Markovnikov product.
Why Does it Follow the Same Rule?
The electrophile adds to the sp2 carbon

bonded to the most hydrogens.

More Reactions

Summary
Addition of Halogens, X2:
◦ Reagent : halogen (e.g. Br2) in an inert solvent
like methylene chloride, CH2Cℓ2.
◦ Reaction proceeds via cyclic halonium ion (i.e.
bromonium or chloronium ion intermediates)
◦ anti addition
Formation of Halohydrins:
◦ bromonium or chloronium ion intercepted by
H2O
◦ Markovnikov's rule apply (with respect to H2O)
◦ anti addition
Exercise
• When cyclohexene is treated with bromine in saturated

aqueous sodium chloride, a mixture of trans-2-
bromocyclohexanol and trans-1-bromo-2-
chlorocyclohexane results. Propose a mechanism to
account for these two products.

Solution to Exercise
Cyclohexene reacts with bromine to give a bromonium ion,
which will react with any available nucleophile. The most
abundant nucleophiles in saturated aqueous sodium chloride
solution are water and chloride ions. Attack by water gives the
bromohydrin, and attack by chloride gives the dihalide. Either of
these attacks gives anti stereochemistry.

Outline
Addition of Hydrogen
Reaction requires molecular hydrogen (H2) and a metal catalyst
◦ Ni, Pd, Pt, Ru typical metals used

◦ Because a gas, liquid and solid metal are used, this reaction is
known as a heterogenous catalysis
◦ both hydrogen atoms add to the same side of the double bond
(syn addition)
Specific example:

catalytic hydrogenation
a reduction reaction
Mechanism for Hydrogen Addition
• Hydrogen (H2) and the alkene are adsorbed on the metal surface.
Once adsorbed, the hydrogens insert across the same face of the
double bond and the reduced product is released from the metal.
• The reaction has a syn stereochemistry since both hydrogens will
add to the same side of the double bond.

Mechanism for Hydrogen Addition
catalytic hydrogenation

Relative Stabilities of Alkenes

Summary Syn & Anti addition

Exercise
Give the product obtained from the reaction of 1-ethylcyclohexene with the following reagents.
Show the stereochemistry if possible.
(a) HBr
(b) H2, Pt/C
(c) BH3/THF followed by –OH, H2O2
(d) Br2/CH2Cℓ2

Oxidation of Alkene-Syn
dihydroxylation
The formation of 1,2-diols (glycols) from alkenes may be carried out in the
following ways:
Osmium Tetroxide (OsO4)

Oxidative Cleavage of C=C with
KMnO4
If the solution is warm or acidic or too concentrated,

oxidative cleavage of the glycol may occur.
Disubstituted carbons become ketones.
Monosubstituted carbons become carboxylic acids.

Oxidative Cleavage of C=C with
KMnO4
Examples:
Aldehyde can be further

oxidized to carboxylic acid!

Oxidative Cleavage of C=C
with Ozone, O3 = Ozonolysis
Ozone will oxidatively cleave (break) the double bond to produce aldehydes and
ketones.
Ozonolysis is milder than KMnO4 and will not oxidize aldehydes to carboxylic
acids.
A second step (2) of the ozonolysis is the reduction of the intermediate by zinc
or dimethyl sulfide.

Comparison of Permanganate
Cleavage and Ozonolysis

Summary
• Osmium tetroxide (OsO4), cold, dilute KMnO4, and

epoxidation oxidize the pi bond of an alkene but
leave the sigma bond intact.
• Ozone and warm, concentrated KMnO4 break the

double bond entirely to give carbonyl compounds.

Exercise and Solution
Ozonolysis–reduction of an unknown alkene
gives an equimolar mixture of
cyclohexanecarbaldehyde and butan-2-one.
Determine the structure of the original alkene.

Exercise and Solution
Solution
We can reconstruct the alkene by removing the
two oxygen atoms of the carbonyl groups (C=O)
and connecting the remaining carbon atoms with
a double bond. One uncertainty remains,
however: The original alkene might be either of
two possible geometric isomers.

Organic Reactions:
Reactions of Alkynes
Addition Reactions:
◦ With two pi bonds, alkynes often mimic the behavior of
alkenes.
◦ presence of the pi bond allows alkynes to undergo electrophilic
addition reactions, using either one or both sets of pi electrons.
◦ These reactions still follow the rules of addition with respect to
carbocation stability – the more substituted carbocation is
formed as the intermediate of the addition reaction.

Reactions of alkynes
Electrophilic addition reactions
• Addition of Hydrogen Halides and Addition of Halogens
•Addition of Water/Hydroboration–Oxidation

Reactions of alkynes

Examples: Addition of HX & X2
Geminal dihalides = compounds that
have two halogen atoms bonded to the
same carbon atom

Reduction/Addition of
Hydrogen
Addition of hydrogen to a triple bond can generate the alkane,
the E alkene or the Z alkene, depending on the reagent.

Addition of Water to an Alkyne
One method of synthesizing ketones.

Hydroboration–Oxidation of Terminal
Alkynes
Bulky borane required to distinguish terminal end from
substituted end:

Formation of Ketone versus Aldehyde


Exercise
What is the major product of each of the following reactions?:
2-methylpropene reacting with:
1) HCℓ
2) HBr
3) Br2 (show the stereochemistry)
4) Cℓ2, H2O
5) H2O, H2SO4
6) CH3OH, H2SO4
Draw the structure of the starting alkene, name the reaction type
and give the IUPAC name of the product in each reaction.

Categories of Organic Reactions
Addition
Substitution: an atom or group of atoms is replaced by another species;
Elimination
Rearrangement

Substitution & Elimination
Reactions
Substitution reaction—the electronegative group

is replaced by another group.
Elimination reaction—the electronegative group

is eliminated along with a hydrogen.
A Substitution Reaction
More precisely called a nucleophilic

substitution reaction because the atom
replacing the halogen is a nucleophile.

Electrophilic Addition Reaction - II

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E

ELECTROPHILIC ADDITION REACTIONS_P.SHANIKA 2

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Note: some electrophiles are neutral and some have a full or

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Note: some nucleophiles are neutral and some have a full or

Bonds broken Bonds formed

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Which process looks more favorable?

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Note: carbocation stability  3 > 2 > 1

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 Markovnikov’s rule is to say that in the addition of HX to an

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☓ (1o cation) fast

(2o cation) fast

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 reaction potentially yield two or more constitutional isomers but

 When alkenes are treated with HBr in the

• Hydrogen is abstracted from HBr.

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Tertiary radical is more stable, so that intermediate forms faster

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Carbocation intermediates (2) have equal stabilities, therefore

(a)CH3CH2CH=CH2 (b) CH3CH=CHCH3

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NOT 1,2-alkyl shift

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