Chapter 4A

Reaction of alkenes

127
Reactions of Alkenes: Addition Reactions
6.1: Hydrogenation of Alkenes – addition of H-H (H2) to the
π-bond of alkenes to afford an alkane. The reaction must be
catalyzed by metals such as Pd, Pt, Rh, and Ni.
H H H H

+
Pd/C
C C
H°hydrogenation = -136 KJ/mol
C C H H H
EtOH H
H H H H

C-C π-bond H-H C-H

= 243 KJ/mol = 435 KJ/mol = 2 x -410 KJ/mol = -142 KJ/mol

• The catalysts is not soluble in the reaction media, thus this

process is referred to as a heterogenous catalysis.
• The catalyst assists in breaking the -bond of the alkene and
the H-H -bond.
• The reaction takes places on the surface of the catalyst. Thus,
the rate of the reaction is proportional to the surface area
of the catalyst.
128
• Carbon-carbon -bond of alkenes and alkynes can be reduced
to the corresponding saturated C-C bond. Other -bond bond
such as C=O (carbonyl) and CN are not easily reduced by
catalytic hydrogenation. The C=C bonds of aryl rings are not
easily reduced.
O O

H2, PtO2

ethanol

O
H2, Pd/C
C5H11 OH CH3(CH2)16CO2H
Linoleic Acid (unsaturated fatty acid) Steric Acid (saturated fatty acid)
O
O
OCH3 H2, Pd/C
OCH3
ethanol

H2, Pd/C C
C
N N
ethanol
129
6.2: Heats of Hydrogenation -an be used to measure relative
stability of isomeric alkenes
H H H CH3
trans isomer is ~3 KJ/mol
H3C CH3 H3C H more stable than the
cis-2-butene trans-2-butene cis isomer
H°combustion : -2710 KJ/mol -2707 KJ/mol
H H H CH3
H2, Pd H2, Pd
CH3CH2CH2CH3
H3C CH3 H3C H

cis-2-butene trans-2-butene

H°hydrogenation: -119 KJ/mol -115 KJ/mol

trans isomer is ~4 KJ/mol more stable than the cis isomer

The greater release

of heat, the less
stable the reactant.

130
Table 6.1: Heats of Hydrogenation of Some Alkenes
Alkene H° (KJ/mol)
H2C=CH2 136

H H
monosubstituted
125 - 126
H3C H

H H
117 - 119
H3C CH3

H CH3
disubstituted 114 - 115
H3C H

H3C H
116 - 117
H3C H

H3C H
trisubstituted 112
H3C CH3

H3C CH3
tetrasubstituted 110
H3C CH3 131
6.3: Stereochemistry of Alkene Hydrogenation
Mechanism:
H H
H2C CH2 H H H2C CH2

H2C CH2
H2

HH
H H
H H C C
C H H H
H H
C H

The addition of H2 across the -bond is syn, i.e., from the

same face of the double bond
H CH3
CH3 H2, Pd/C CH3 H

EtOH CH3
CH3 CH3
H H

syn addition
of H2 Not observed
132
6.4: Electrophilic Addition of Hydrogen Halides to Alkenes

C-C -bond: H°= 368 KJ/mol

C-C -bond: H°= 243 KJ/mol

-bond of an alkene can

act as a nucleophile!!

Electrophilic addition reaction

H H Br H
C C + H-Br C C
H H
H H H H
nucleophile electrophile

Bonds broken Bonds formed

C=C -bond 243 KJ/mol H3C-H2C–H -410 KJ/mol
H–Br 366 KJ/mol H3C-H2C–Br -283 KJ/mol
calc. H° = -84 KJ/mol
133
expt. H°= -84 KJ/mol
Reactivity of HX correlates with acidity:
HF << HCl < HBr < HI fastest
slowest
6.5: Regioselectivity of Hydrogen Halide Addition:
Markovnikov's Rule H
C H H-Br Br H H Br
R C R C C H + R C C H
H H H H H
none of this
R
H-Br Br H H Br
C H +
R C R C C H R C C H
H R H R H
none of this
R
Br H H Br
C H H-Br
R C R C C R + R C C R
R R H R H
none of this
R
Br H H Br
C H H-Br
H C R C C R + R C C R'
R' H H H H
Both products observed

For the electrophilic addition of HX across a C=C bond, the H (of

HX) will add to the carbon of the double bond with the most H’s
(the least substitutent carbon) and the X will add to the carbon of
134
the double bond that has the most alkyl groups.
Mechanism of electrophilic addition of HX to alkenes

6.6: Mechanistic Basis for Markovnikov's Rule:

Markovnikov’s rule can be explained by comparing the
135
stability of the intermediate carbocations
For the electrophilic addition of HX to an unsymmetrically
substituted alkene:
• The more highly substituted carbocation intermediate is
formed.
• More highly substituted carbocations are more stable than
less substituted carbocations. (hyperconjugation)
• The more highly substituted carbocation is formed faster
than the less substituted carbocation. Once formed, the
more highly substituted carbocation goes on to the final
product more rapidly as well.

136
6.7: Carbocation Rearrangements in Hydrogen Halide
Addition to Alkenes - In reactions involving carbocation
intermediates, the carbocation may sometimes rearrange if a
more stable carbocation can be formed by the rearrangement.
These involve hydride and methyl shifts.
H
Cl H
H H
H3C C H H-Cl H3C C H
+ H3C C H
C C C C
C C
H3C H3C H
H H H H H3C H
Cl H

~ 50% ~ 50%
expected product
H
Cl H
H3C H
H3C C H H-Cl H3C C H
+ H3C C H
C C C C
C C
H3C H3C H
CH3 H CH3 H H3C H
Cl H

Note that the shifting atom or group moves with its electron pair.
A MORE STABLE CARBOCATION IS FORMED. 137
6.8: Free-radical Addition of HBr to Alkenes
H
Br H H Br
C H H-Br + Polar mechanism
H3CH2C C H3CH2C C C H H3CH2C C C H
H H H H H
(Markovnikov addition)
none of this
H
Br H H Br
C H H-Br + Radical mechanism
H3CH2C C H3CH2C C C H H3CH2C C C H
H peroxides H H H H
(Anti-Markovnikov addition)
(RO-OR)
none of this

H H-Br Br H H Br
C H R C C H + R C C H
R C
H
ROOR H H H H The regiochemistry of
(peroxides) none of this
R
HBr addition is reversed
H-Br Br H H Br
C H R C C H + R C C H in the presence of
R C
H
ROOR R H R H peroxides.
none of this
R
Br H H Br
R
C
C
H H-Br + Peroxides are radical
R C C R R C C R
R ROOR R H R H initiators - change in
none of this mechanism
R
Br H H Br
C H H-Br
H C R C C R + R C C R'
R' ROOR H H H H
138
Both products observed
The regiochemistry of free radical addition of H-Br to alkenes
reflects the stability of the radical intermediate.
H H R
R C• R C• R C•
H R R
Primary (1°) < Secondary (2°) < Tertiary (3°)

139
6.9: Addition of Sulfuric Acid to Alkenes
Reaction type: Electrophilic Addition
When treated with aq. acid, most commonly H2SO4, alkenes form alcohols.
Electrophile : H+
Regioselectivity predicted by Markovnikov's rule
Reaction proceeds via protonation to give the more stable carbocation
intermediate.
Not stereoselective since reactions proceeds via a planar carbocation.

140
6.10: Acid-Catalyzed Hydration of Alkenes - addition of water
(H-OH) across the -bond of an alkene to give an alcohol;
opposite of dehydration

H3C H3C
H2SO4, H2O
C CH2 C OH
H3C
H3C H3C

This addition reaction follows Markovnikov’s rule The more

highly substituted alcohol is the product and is derived from
The most stable carbocation intermediate.

Reactions works best for the preparation of 3° alcohols

141
6.11: Thermodynamics of Addition-Elimination Equlibria
H3C H3C
H2SO4

C CH2 + H2O C OH
H3C
H3C H3C

Bonds broken Bonds formed

C=C -bond 243 KJ/mol H3C-H2C–H -410 KJ/mol
H–OH 497 KJ/mol (H3C)3C–OH -380 KJ/mol
calc. H° = -50 KJ/mol

G° = -5.4 KJ/mol H° = -52.7 KJ/mol S° = -0.16 KJ/mo

How is the position of the equilibrium controlled?

Le Chatelier’s Principle - an equilibrium will adjusts to any stress
The hydration-dehydration equilibria is pushed toward hydration
(alcohol) by adding water and toward alkene (dehydration) by
removing water 143
The acid catalyzed hydration is not a good or general method for
the hydration of an alkene.
Oxymercuration: a general (2-step) method for the Markovnokov
hydration of alkenes
H H OH H OH
C H 1) Hg(OAc)2, H2O 2) NaBH4
C Hg(OAc) C H
C4H9 C C4H9 C C4H9 C
H H H H H
O NaBH4 reduces the C-Hg
Ac= acetate =
H3C
C
O
bond to a C-H bond

144
6.12: Hydroboration-Oxidation of Alkenes - Anti-Markovnikov
addition of H-OH; syn addition of H-OH
CH3 1) B2H6, THF H
2) H2O2, NaOH, H2O CH3

H
HO
6.13: Stereochemistry of Hydroboration-Oxidation
6.14: Mechanism of Hydroboration-Oxidation -
Step 1: syn addition of the H2B–H bond to the same face of the
-bond in an anti-Markovnikov sense; step 2: oxidation of the
B–C bond by basic H2O2 to a C–OH bond, with retention of
stereochemistry

145
 6.15: Addition of Halogens to Alkenes
X2 = Cl2 and Br2
X2 X X
C C C C (vicinal dihalide)

alkene 1,2-dihalide

6.16: Stereochemistry of Halogen Addition - 1,2-dibromide

has the anti stereochemistry
Br Br
+ Br2 +
Br Br

not observed

Br
CH3 CH3
Br2

Br
H
146
6.17: Mechanism of Halogen Addition to Alkenes:
Halonium Ions - Bromonium ion intermediate explains the
stereochemistry of Br2 addition

147
 6.18: Conversion of Alkenes to Vicinal Halohydrins
"X-OH" X OH
C C C C

alkene halohydrin

X2, H2O X
+ HX
OH

anti
stereochemistry

Mechanism involves a halonium ion intermediate

148
For unsymmterical alkenes, halohydrin formation is
Markovnikov-like in that the orientation of the addition of
X-OH can be predicted by considering carbocation stability

 CH3
more + charge on the
Br 
+
more substituted carbon


H2O adds in the second step and adds to the

carbon that has the most + charge and ends
up on the more substituted end of the double bond

HO
CH3 CH3
Br2, H2O
+ HBr
Br
H

Br adds to the double bond first (formation of

bromonium ion) and is on the least substituted
end of the double bond 149
Organic molecules are sparingly soluble in water as solvent. The
reaction is often done in a mix of organic solvent and water using
N-bromosuccinimide (NBS) as he electrophilic bromine source.
O OH O

Br
DMSO, H2O N H
+ N Br +

O O

Note that the aryl ring does not react!!!

6.19: Epoxidation of Alkenes - Epoxide (oxirane): three-

membered ring, cyclic ethers.
O H O

Reaction of an alkene with a peroxyacid: H3C O

O
H3C OH
HO OH

peroxyacetic acid peroxyacetic acetic peroxide

acid acid

O H
OH
O
H3C O + O
H3C O

150
Stereochemistry of the epoxidation of alkenes: syn addition of
oxygen. The geometry of the alkene is preserved in the product
Groups that are trans on the alkene will end up trans on the
epoxide product. Groups that are cis on the alkene will end
up cis on the epoxide product.
H H H3CCO3H O
H H
R R R R
cis-alkene cis-epoxide

H R H3CCO3H O
H R
R H R H
trans-alkene trans-epoxide

6.20: Ozonolysis of Alkenes - oxidative cleavage of an alkene

to carbonyl compounds (aldehydes and ketones). The - and
-bonds of the alkene are broken and replaced with C=O
double bonds.
C=C of aryl rings, CN and C=O do not react with ozone, 151
CC react very slowly with ozone
 electrical +
Ozone (O3): 3 O2 discharge
2 O3 O _
O O

mechanism
O3, CH2Cl2 O
R1 R3 -78 °C O O O O R1 R3
R1 R3 Zn
-or- O + O
R2 R4 R1 R3 R2 R4
O (H3C)2S R2 R4
R2 R4
molozonide ozonide + ZnO or (H3C)SO

1) O3
2) Zn
O + O

1) O3
2) Zn H
H + O C
H
O

1) O3
2) Zn O

H
O

152
153
154