Chapter 5

Reactions of Alkenes and Alkynes

Characteristic Reactions of Alkenes
Addition to the carbon–carbon double bond :
π bond is broken and, in its place, sigma bonds
are formed to two new atoms or groups of
atoms.
Low Mwt alkenes undergo polymerization
reaction
 Reaction Mechanism
A reaction mechanism is a step-by-step description of how a chemical reaction occurs:
• Which bonds are broken and which new ones are formed.
• The order in which bond-breaking and bond-forming steps take place.
• The role solvent and of the catalyst (if any is present).
• The energy of the entire system during the reaction.
Reaction mechanism is a hypothesis, which can be confirmed by experimental evidence.
Bond breaking corresponds to an increase in energy, and bond forming corresponds to a
decrease in energy.
Energy Diagram
Energy diagram: A graph showing the changes in energy that occur during a chemical
reaction; energy is plotted in the y-axis and progress of the reaction (reaction coordinate)
is plotted in the x-axis.
Heat of reaction H:The difference in energy between reactants and products.
• Exothermic: The products of a reaction are lower in energy than the reactants; heat is
released.
• Endothermic: The products of a reaction are higher in energy than the reactants; heat is
absorbed.
 Activation energy Ea: The difference in energy
between the reactants and the transition state.It is
the minimum energy required for a reaction to
occur.
Ea determines the rate of reaction.
• If Ea is large very few molecular
collisions occur with sufficient energy to
reach the transition state, and the reaction
exothermic reaction is slow.
• If Ea is small many collisions generate
sufficient energy to reach the transition
Figure 5.1 An energy diagram for a one-step reaction between C and
A-B to give C-A and B. state, and the reaction is fast.
Transition state: An unstable species of maximum
energy formed during the course of a reaction; a
maximum on an energy diagram. We cannot isolate it
and we cannot determine its structure experimentally.
Its lifetime is on the order of a picosecond
Figure 5.2 An energy diagram for a two-step reaction
involving formation of an intermediate.
• The intermediate is highly reactive, and
rarely, if ever, can one be isolated.
• In this example, step 1 crosses the higher energy
barrier and is, therefore, the rate-determining step.
 Electrophilic Additions to Alkenes
• Nucleophile (nucleus loving) an electron-rich species , it seeks a region of low electron
density.
• Electrophile (electron loving) a low-electron-density species, it seeks a region of high
electron density.
• Note that nucleophiles are Lewis bases and electrophiles are Lewis acids
• Hydrohalogenation: Addition of hydrogen halides (HCl, HBr, HI)
• Acid-Catalyzed hydration: Addition of water (H2O/H2SO4)
• Halogenation: Addition of halogens (Cl2, Br2)
Addition of HX
• Carried out with the pure reagents or in a polar solvent such as acetic acid.
H Cl
CH2 =CH2 + HCl CH2 -CH2
Ethylene Chloroeth ane
(Ethyl chloride)
Addition is regioselective: A reaction in which one direction of bond-forming or bond-breaking
occurs in preference to all other directions.
Cl H H Cl
CH3 CH=CH2 + HCl CH3 CH-CH2 + CH3 CH-CH2
Prop ene 2-Chloropropane 1-Ch loroprop ane
(not ob served )
(Isopropyl chloride)

Markovnikov’s rule: In additions of HX to a double bond, H adds to the carbon with the
greater number of hydrogens bonded to it.
 Addition of HCl to 2-Butene Carbocation: A species
containing a carbon atom that has
• A two-step mechanism only six electrons in its valence
• Step 1: Formation of a sec-butyl cation, a 2° carbocation shell and bears a positive charge.
intermediate. They are Lewis acids and
electrophiles
Carbocations are:
Classified as 1°, 2°, or 3°
depending on the number of
carbons bonded to the carbon
• Step 2: Reaction of the sec-butyl cation (an electrophile) bearing the positive charge.
with chloride ion (a nucleophile) completes the reaction.
• Bond angles about the
positively charged carbon
are approximately 120°.
• Carbon uses sp2 hybrid
orbitals to form sigma
bonds to the three
attached groups.
The unhybridized 2p orbital lies perpendicular to the sigma bond framework and contains no
electrons.

Figure 5.4 An energy diagram for the two-step addition of

HCl to 2-butene. The reaction is exothermic.
 Carbocations
• 3°carbocation is more stable than a 2° carbocation, and requires a lower activation energy for its
formation.
• 2°carbocation is, in turn, more stable than a 1° carbocation, and requires a lower activation energy
for its formation.
• Methyl and 1°carbocations are so unstable that they are never observed in solution.

Inductive effect: The polarization of the electron density of a covalent bond as a result of the electronegativity of a
nearby atom.
• The electronegativity of a carbon atom bearing a positive charge exerts an electron-withdrawing inductive
effect that polarizes electrons of adjacent sigma bonds toward it.
• the positive charge of a carbocation is not localized on the trivalent carbon, but rather is delocalized over
nearby atoms as well.
• The larger the area over which the positive charge is delocalized, the greater the stability of the cation.
• As number of alkyl groups bonded to the cation carbon increases, the stability of the cation will increases.
Figure 5.5 Delocalization of positive
charge by the electron-withdrawing
inductive effect of the positively
charged trivalent carbon according to
molecular orbital calculations.
Step 1

Step 2
 Addition of H2O to an Alkene
Addition of H2O to an alkene is called hydration.
Acid-catalyzed hydration of an alkene is regioselective: hydrogen adds preferentially to the
less substituted carbon of the double bond. Thus H-OH adds to alkenes in accordance with
Markovnikov’s rule. CH3 CH3
OH H H2 SO4
H2 SO4 CH3 C=CH2 + H2 O CH3 C-CH2
CH3 CH=CH2 + H2 O CH3 CH-CH2
HO H
Prop ene 2-Prop anol
2-Methylprop ene 2-Methyl-2-propanol
 Addition of Cl2 and Br2
Carried out with either the pure reagents or in an inert solvent such as CH2Cl2or CCl4
Br Br
CH3 CH=CHCH3 + Br2 CH3 CH-CHCH3
CH2 Cl2
2-Butene 2,3-Dibromobutane
• Addition is stereoselective.
Stereoselective reaction: A reaction in which one stereoisomer is formed or destroyed in
preference to all others that might be formed or destroyed.
Addition to a cycloalkene, for example, gives only a trans product. The reaction occurs
with Br
+ Br2
• anti stereoselectivity. CH2 Cl2
Br
Cyclohexen e t rans -1,2-D ib romocycloh exane
Bromine test is a very important identification test of alkenes
Step 1: Formation of a bromonium ion intermediate

Step 2: Halide ion opens the three-membered ring

 anti and coplanar.
Carbocation Rearrangements
In the addition of HCl to 3,3-dimethyl-1-butene only 17% of 2-chloro-3,3-dimethylbutane, the
expected product, is formed. The major product is 2-chloro-2,3-dimethylbutane, a compound with a
different connectivity of its carbon atoms than that in the starting material. We say that the formation of 2-
chloro-2,3-dimethylbutane involves a rearrangement.
Rearrangement A reaction in which a carbon or hydrogen atom has shifted its connectivity to
another atom within the molecule.
This type of rearrangement called a 1,2-shift.
Step 1: Proton transfer from the HCl to the alkene to give a 2° carbocation intermediate
+
+ H Cl + Cl

3,3-Dimethy-1-butene A 2° carbocation
intermediate
Step 2: Migration of a methyl group with its bonding electrons from the adjacent carbon gives a
more stable 3°carbocation. The two electrons in
+
this bond move to
the electron-deficient +
carbocation.

A 2° carbocation A 3° carbocation
intermediate intermediate

Step 3: Reaction of the 3°carbocation (an electrophile and a Lewis acid) with chloride ion (a
nucleophile and a Lewis base) gives the rearranged product.
Cl
+
Cl
+

A 3° carbocation
inte rme diate
Note: 1° Carbocations are never observed for reactions taking place in solution and should not be
proposed as reaction intermediates.

Rearrangements also occur in the acid-catalyzed hydration of alkenes, especially where the
carbocation formed in the first step can rearrange to a more stable carbocation.
This H migrates
to an adjacent
carbon
CH3 CH3
H3O+
CH3 CHCH= CH2 + H2 O CH3 CCH2 CH 3
OH
3-Methyl-1-butene 2-Methyl-2-butanol

+ O H
H 3O
H 2O
+
2-Methyl-2-butanol
3-Methyl-1-butene
 Hydroboration-Oxidation
• The result of hydroboration followed by oxidation of an alkene is hydration of the carbon-
carbon double bond. 1. BH3
OH
2. NaOH, H2 O2 1-Hexanol
1-Hexene
• Because -H adds to the more substituted carbon of the double bond and -OH adds to the less
substituted carbon, we refer to the regiochemistry of hydroboration/oxidation as anti-
Markovnikov hydration.
• Borane is most commonly used as a solution of BH3 in tetrahydrofuran (THF).
O + -
+ B2 H6
••
••
2 O BH3

••
2

Tetrahydrofuran BH3 •THF

(THF)

• Hydroboration is the addition of BH3 to an alkene to form a trialkylborane.

Hydroboration is both regioselective and syn stereoselective.
• Regioselectivity: -H adds to the more substituted carbon and boron adds to the less substituted
carbon of the double bond.
• Stereoselectivity: Boron and -H add to the same face of the double bond (syn
stereoselectivity). CH3 CH3
CH3
H H
+ BH3 +
BR2 BR2
1-Methylcyclopentene H H
(Syn addition of BH 3)
(R = 2-methylcyclopentyl)
• Chemists account for the regioselectivity by proposing the formation of a cyclic four-center
transition state.
• And for the syn stereoselectivity by steric factors. Boron, the larger part of the reagent, adds to
the less substituted carbon and hydrogen to the more substituted carbon.
 
H B
H B
CH3 CH2 CH2 CH=CH2 CH3 CH2 CH2 CH-CH2
Trialkylboranes are rarely isolated. Treatment with alkaline hydrogen peroxide (H2O2/NaOH),
oxidizes a trialkylborane to an alcohol and sodium borate.
(RO) 3 B + 3NaOH 3ROH + Na3 BO3
A trialkylborate Sodium
borate
Reduction of alkene to an alkane
The process is called catalytic reduction or, alternatively, catalytic hydrogenation.

Catalytic reduction is stereoselective, the most common pattern being the syn addition
of hydrogens to the carbon–carbon double bond.
• The reduction of an alkene to an alkane is an exothermic process (stronger bonds are formed).
• The greater the substitution, the lower is the heat of hydrogenation.
• The heat of hydrogenation of a trans alkene is lower than that of the isomeric cis alkene.

Ozonolysis of an Alkene
CH3 O O O
1 . O3
CH3 C=CHCH2 CH3 CH3 CCH3 + HCCH2 CH3 + CH3 -S-CH3
2 . ( CH3 ) 2 S
2-Methyl-2-penten e Propanone Propanal Dimethylsu lfoxide
(a ketone) (an ald ehyd e) (D MSO)
 • Ozone (18 valence electrons) is strongly electrophilic.
O O O O
O O O O O O O O

Ozone is strongly electrophilic

because of the positive formal
charges on the two end oxygens.

• Initial reaction gives an intermediate called a molozonide.

O
O O
O O
O O O O

A molozonide
• The intermediate molozonide rearranges to an ozonide.
• Treatment of the ozonide with dimethylsulfide gives the final products.
O H H
O O O O
O3 C C (CH3 ) 2 S
CH3 CH=CHCH3 CH3 CH-CHCH3 H3 C CH3 2 CH3 CH
O O
2-Butene A mol ozo nid e A n o zoni de A cetal dehy de
 Reactions of alkynes
1. Acetylide Anions in Synthesis
• An acetylide anion is both a strong base and a nucleophile. It can donate a pair of electrons
to an electrophilic carbon atom and form a new carbon-carbon bond.

This reaction is called alkylation

2. Acid-Catalyzed Hydration of Alkynes

In the presence of concentrated sulfuric acid and Hg(II) salts, alkynes undergo hydration in accordance
with Markovnikov’s rule.
The initial product is an enol, a compound containing an hydroxyl group bonded to a carbon-carbon
double bond.
The enol is in equilibrium with a more stable keto form. This equilibration is called keto-enol
tautomerism.
 H2 SO4 OH O
CH3 C CH + H2 O CH3 C=CH2 CH3 CCH3
Hg SO4
Propyne Propen-2-ol Propanone
(an enol) (Acetone)
3. Reduction of Alkynes
a. Treatment of an alkyne with H2 in the presence of a transition metal catalyst results in addition
of two moles of H2 and conversion of the alkyne to an alkane.

b. By the proper choice of catalyst it is possible to stop the reaction at the addition of one mole of
H2. The most commonly used catalyst for this purpose is the Lindlar catalyst(finely powdered
palladium metal deposited on solid calcium carbonate) . This reduction is syn stereoselective.

c. Reduction of an alkyne using an alkali metal (Li, Na, or K) in liquid ammonia is anti
stereoselective and gives a trans alkene Li H 3C H
H 3C C C CH 2 CH 3
N H 3(l) H CH 2 CH 3
2-Pentyne
trans-2-Penene