Alkenes and Alkynes

Addition Reaction
Characteristic reaction of compounds with C=C bonds.
General type below:
H H H H
+ A–B H H
H H A B
 Anatomy of an Addition Reaction.
An addition reaction results in the conversion of one π-bond
and one σ-bond into two σ-bonds. This is energetically
favorable because σ-bonds are stronger than π-bonds.
Addition reactions are usually exothermic.
Electrophiles
π-Bond is susceptible to electron-seeking reagents. These
reagents called electrophiles (or said to be electrophilic). Any
reaction involving an electrophile also involves a nucleophile

Electrophiles are Lewis Acids : they can accept an

electron pair.
Some electrophiles: H+, Br2 (can be polarized so one end is
positive), BF3, AlCl3.
 Addition of Hydrogen Halides to Alkenes :
Markovnikov’s Rule
Hydrogen halides add to the double bond of alkenes.
C C + H–X C C

H X
The order of reactivity is :
HI > HBr > HCl > HF
HCl does not react fast enough to be useful as a preparative
method. This can be remedied by adding silica gel or alumina
to the mixture.
Addition to unsymmetrical alkenes could give two possible
products : H
H
H

+ H–X Br
+ Br
H
product not formed
Mechanism of Addition
Step 1 : Formation of Carbonation.

Step 2 : Bromine Nucleophile attacks carbocation.

Free Energy Diagram of Reaction

 Markovnikov’s Rule.
“In the ionic addition of an unsymmetrical reagent to a double
bond, the positive portion of the reagent attaches itself to a
carbon atom of the double bond so as to yield the more stable
carbocation as an intermediate”.
Another example :
H Cl I
δ+ δ-
+ I–Cl
H

Regioselective Reactions.
When a reaction that can potentially yield two or more
constitutional isomers actually only produces one (or
predominantly one), it is said to be regioselective.
Markovnikov addition is regioselective.
 Stereochemistry of the HX Addition
When the addition of HX to a double bond produces an alkyl
halide that has a stereocenter, the product will exist as a pair of
enantiomers.
*
CH3CH2C=CH2 + HX CH3CH2CHCH3
X
The reason is that the nucleophile (Nu–) can attack the
carbocation (which is trigonal planar ⇒ achiral) from the top
or bottom of the plane the molecule resides in.
 Addition of Sulfuric Acid to Alkenes.
When alkenes treated with cold concentrated sulfuric acid they
react by addition to form alkyl hydrogen sulfates.

+ H2SO4 OSO 3H

Reaction mechanism
Step 1: Alkene accepts a proton from acid

Step 2: Carbocation reacts with hydrogen sulfate ion to form

product
Same steps as HX addition, also follows Markovnikov’s rule.
Most stable carbocation reacts the fastest, and predominates as
the product. Regioselective reaction.

Alkyl Hydrogen sulfates can easily be hydrolyzed by heating

them with water.
cold
CH3CH=CH2 CH3CHCH3
H2SO4
OSO3H

H2O, heat
CH3CHCH3 + H2SO4
OH
Overall result is Markovnikov addition of water
 Addition of Water to Alkenes : Acid-Catalyzed Hydration.
→ Acid-catalyzed addition of H2O to double bonds used in
large-scale industry for the preparation of low molecular
weight alcohols.
H3O+
+ H2O OH
25 ºC

→Typical acids used are dilute solutions of H2SO4 and

H3PO4.
→ Reaction follows Markovnikov’s rule so the acid-catalyzed
hydration only yields 1° alcohols in one case.
H3O+
H2C=CH2 + H2O CH3CH2OH
300 ºC
Mechanism.
The mechanism is simply the reverse for the dehydration of an
alcohol.
Step 1 : Formation of Carbocation.

Step 2 : Carbocation is attacked by H2O.

Step 3 : Proton transfer leads to product.

The equilibrium of this reaction can be controlled by the
conditions employed :
i) For alcohol dehydration to give an alkene, a concentrated
solution of acid is used. The concentration of H2O is low in
this case. Water can also be removed by distillation, hence
use of high temperature.
ii) For alkene hydration to give an alcohol, a dilute solution
of acid is used, so that the concentration of water is high.
Low temperature also favour alcohol product.
→ Alkene hydrations can give rearrangement products. If
carbocation formed can rearrange to a more stable form, this
will occur. This limits the synthetic use of this reaction.
OH
H2SO4
H2O
 Addition of Bromine and Chlorine to Alkenes.
Alkenes react rapidly with chlorine and bromine is non-
nucleophilic solvent to form vicinal dihalides.

- 9 ºC
CH3CH=CH2 + Cl2 CH3CHCH2
CCl4
Cl Cl

Br Br

+ Br2 - 9 ºC H H
H H
CCl4 Br Br

trans-1,2-Dibromocyclohexane
racemic

Addition is always anti.

 Mechanism for Addition of Br2
Step 1: Polarization of Br2 molecule. Alkene attacks,
bromonium ion formed. Bromide leaves.

Step 2 : Bromide nucleophile attacks bromonium ion in SN2

mechanism. Ring opens to form vic-dibromides.
Stereochemical Considerations.
Br Br

+ Br2 - 9 ºC H H
H
CCl4 Br
H
Br

The SN2 attack inverts the configuration of the carbon being

attacked. Since the bromide nucleophile can attack at either
carbon attached to the bromonium ion, a pair of enantiomers
are possible as products.
Stereospecific Reaction.
A reaction is stereospecific when a particular stereoisomeric
form of the starting material reacts to give a specific
stereoisomeric form of the product.
Consider the halogen addition of diastereomers trans-2-butene
and cis –2-butene.
trans-2-butene only gives meso compound.
cis-2-butene only gives racemic (2R,3R)- and (2S,3S)-2,3-
dibromobutane.
Stereochemistry controlled by SN2 attack.
 Halohydrin Formation.
If halogenation of an alkene is carried out in an aqueous
solution, the major product is a halo alcohol or halohydrin.

C C + X2 + H20 C C + C C
X X X OH

(minor) (major)
Mechanism
Step 1: The same as for halogen addition. The halonium ion is
formed.
Step 2: H2O molecule acts as a nucleophile, SN2 mechanism,
ring opening halonium ion to give a protonated halohydrin.
Concentration of water far greater than the X-, so the
halohydrin product predominates.

Step 3: Proton transfer to a molecule of water.

If alkene is unsymmetrical, follows Markovnikov’s rule, the
halogen ends up in the least substituted carbon, and the
alcohol in the most.
 Addition of Bromine and Chlorine to Alkynes.
Alkynes show same reactivity towards Br2 and Cl2 than
alkenes do. They react by addition.
Alkynes can have double additions depending on the
stoichiometry used:
2 mol. equivalent of Br2
Br Br Br
Br2 Br2
C C C C C C
CCl4 CCl4 Br Br
Br

It is possible to make a dihaloalkene by adding 1 mol

equivalent of Br2. HO 2C Br
HO2CC≡CCO2H + Br2 C C 70 %
Br CO 2 H

Most additions of chlorine and bromine are anti additions and

yield trans-dihaloalkenes.
 Addition of Hydrogen Halides to Alkynes.
Alkynes react with HCl or HBr to form haloalkenes or
geminal dihalides depending on whether one or two molar
equivalents of hydrogen halide used. Both additions are
regioselective and follow Markovnikov’s rule.
HX X HX H X
C C C C
C C
H H X

The hydrogen atom becomes attached to C-atom that has the

greater number of H-atoms.
C 4H 9 Br
HBr HBr
C4H9C≡CH C CH2 C 4H 9 C CH3
Br Br
Additions can be accelerated by adding acetyl bromide and
alumina instead of HBr. Acetyl bromide reacts with alumina to
generate HBr.
 Oxidation of Alkenes : Syn Hydroxylation.
Alkenes can be oxidized to 1,2-diols, or glycols. Typical
reagents used are potassium permanganate, osmium tetroxide.

cold H 2C CH2
H2C=CH2 + KMnO4 OH OH
-OH, H2O

1. OsO4, pyridine CH3CH CH2

CH3CH=CH2
2. NaSO3/H2O OH OH
or NaHSO3/H2O
Mechanism of Oxidation:
Both permanganate ion, MnO4-, and osmium tetroxide
oxidation first involve the formation of a intermediate with the
alkene.

The cyclic intermediates are then broken down in a series of

oxygen-metal cleavage steps, ultimately producing the glycol.
The reaction, due to the formation of the cyclic intermediate
adds the two -OH groups syn to each other (not anti).

OsO4 gives better yields, but is highly toxic and expensive.

KMnO4 is a powerful oxidizing agent and can result in the
further oxidation of the glycol. Cold, dilute, basic solutions
required. Even so, yields can be low.
 Oxidative Cleavage of Alkenes.
1)When monosubstituted alkenes are treated with hot basic
permanganate solutions, they oxidatively cleave to salts of
carboxylic acids.

Acidification of solution releases 2 mol of acetic acid for each mol

of 2-butene.
2) Alkenes with terminal CH2 group completely oxidize to carbon
dioxide and water.
3) Disubstituted carbon atoms becomes the carbonyl group of a
ketone.

Oxidative cleavage of alkenes can be used to establish location

of the double bond in the alkene chain or ring.
 Ozonolysis of Alkenes.
Ozone (O3) is a more widely reagent to locate the double bond
of an alkene. Ozone reacts with alkenes to form unstable
compounds called ozonides.
O
CH2Cl2
C C + O3
-78 ºC O O
Ozonide
Mechanism
Ozone adds to alkene to create an intermediate ozonide. This
initial ozonide spontaneously fragments. These fragments then
recombine to yield final ozonide product.
Ozonides are very unstable, and low molecular weigh
compounds often explodes. They are thus treated with zinc in
acetic acid (HOAc) to reduce them to carbonyl compound
(either aldehydes or ketones).

p348

Notice, unlike with MnO4-, alkenes with –H attached not lead

to the carboxylic acid.
 Oxidative Cleavage of Alkynes.
Alkynes react with ozone (O3) or with basic potassium
permanganate by cleavage at the carbon-carbon triple bond.
The products in both cases are carboxylic acids.
O O
R C C R1 (a) or (b)
R
C
OH
+ HO
C
R1
(a) 1. O3 2. AcOH
(b) 1. KMnO4 , -OH 2. H+
1. O3 O
CH3(CH2)3C≡CH CH3(CH2)2CH2CO2H + C
2. AcOH HO OH
Pentanoic Acid
Carbonic acid
 Hydrogenation of Alkenes
Alkenes react with hydrogen in the presence of a variety of
finely divided catalysts. The reaction is an addition reaction.
One atom of hydrogen adds to each carbon atom of the double
bond.
CH3CH=CH2 + H2 Ni, Pd CH3CH2CH3
or Pt
25 ºC

Without the catalyst hydrogenation does not take place, even

though the reaction is exothermic (∆Hº = ∼120 kJmol-1). This
is due to the high activation energy of the reaction. The
catalyst provides an alternate pathway of lower free energy of
activation
Free Energy Diagram of Catalytic Hydrogenation
Mechanism Pt
C C C C
+ H H
H–H

310

The catalyst (platinum, nickel, palladium, rhodium, and

ruthenium) absorb hydrogen on their surfaces. The alkene
also gets absorbed and in a stepwise fashion both hydrogens
are added to the same face of the alkene. This is a syn
addition. The alkane then dissociates away from the surface
 Hydrogenation of Alkynes
Depending on catalyst and conditions, one or two mols of
hydrogen will add to the alkyne. If platinum catalyst is used
alkyne reacts with two molar equivalents to give an alkane.
Pt Pt
CH3C≡CCH3 [CH3CH=CHCH3] H CH3CH2CH2CH3
H2 2

Syn Addition of Hydrogen

Ni2B, a nickel boride compound is known as the P-2 catalyst.
It is able to hydrogenate alkynes to give cis alkenes through
syn addition.
H2/Ni2B
CH3CH2C≡CCH2CH3 C C
syn addition H H

(Z)-3-hexene
Anti Addition of Hydrogen
An anti addition of hydrogen atoms to alkynes occurs
when reacted with lithium or sodium metal in ammonia (or
ethylamine) at low temperatures. Trans-alkenes are
produced.
 Questions from Wade

8.1; 8.6; 8.21; 8.22; 8.34; 8.39; 8.37; 8.47(a, b, c, h, I, k, l, m,

n, q); 8.48(b, c, e); 8.82; 8.63; 8.67; 8.68; 8.69 (skip f)
9.12 (skip c); 9.15; 9.24; 9.32; 9.38.
Questions from Solomon
8.2; 8.3; 8.15; 8.20; 8.21; 8.28 (skip c); 8.31; 8.33(skip d);
8.37; 8.39; 8.45; 8.48; 8.52; 8.62.
Questions from Klein
There is some overlap with Lecture 9 (Alcoholc and Ethers), so if you
see a reaction or a reagent that you don’t recognize wait till we cover it.
9.49; 9.51; 9.60; 9.68; 9.70; 9.71; 9.76; 9.79; 9.83; 9.84; 9.86;
9.90; 10.37; 10.45; 10.50; 10.60; 10.62; 10.68; 10.70; 10.77.