Alkenes: Reactions and Synthesis

2302261
Dr Anawat Ajavakom

Diverse Reactions of Alkenes

Alkenes react with many electrophiles to give useful

products by addition (often through special reagents)

alcohols (add H-OH)

alkanes (add H-H)
halohydrins (add HO-X)
dihalides (add X-X)
halides (add H-X)
diols (add HO-OH)
cyclopropane (add :CH2)

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Preparation of Alkenes: A Preview of

Elimination Reactions

Alkenes are commonly made by

1. elimination of HX from alkyl halide (dehydrohalogenation)
Uses heat and KOH

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-Elimination

E1 (Elimination unimolecular)

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E1 (Elimination unimolecular)
Stability of carbocation

3
o

Reactivity of alkyl halide

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E1 (Elimination unimolecular)

-hydrogen

Rearrangement

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E2 (Elimination bimolecular): anti-elimination

Leaving group
I- > Br- > Cl- > F-

Reactivity of alkyl halide

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Preparations of Alkenes

2. elimination of H-OH from an alcohol (dehydration)

require strong acids (sulfuric acid, 50 C) : E1

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Preparations of Alkenes

2. Dehydration of alcohols
+

1,2-Hydride shift
+

1,2-alkyl shift
+

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Preparations of Alkenes

3. Dehalogenation of Dihalide: E2 mechanism

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Preparations of Alkenes

4. Hydrogenation of alkynes and Reduction with Na/NH3

trans
2
2
2

cis

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Reduction with Na/NH3 Mechanism

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Preparations of Alkenes

4. Hydrogenation and reduction of alkynes

5. Pyrolysis of alkane

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Reactions of alkenes:
A. Addition reaction of alkenes
1. Addition of hydrogen halides to alkenes

General reaction mechanism: electrophilic addition

Attack of electrophile (such as HBr) on bond of alkene
Produces carbocation and bromide ion
Carbocation is an electrophile, reacting with nucleophilic
bromide ion

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Example of Electrophilic Addition

Addition of hydrogen
bromide to 2-Methylpropene
H-Br transfers proton to
C=C
Forms carbocation
intermediate
More stable cation
forms
Bromide adds to
carbocation

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Orientation of Electrophilic Addition:

Markovnikovs Rule

In an unsymmetrical alkene, HX reagents can add in two

different ways, but one way may be preferred over the
other

If one orientation predominates, the reaction is

regiospecific

Markovnikov observed in the 19th century that in the

addition of HX to alkene, the H attaches to the carbon
with the most Hs and X attaches to the other end (to the
one with the most alkyl substituents)
This is Markovnikovs rule
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Example of Markovnikovs Rule

Addition of HCl to 2-methylpropene

Regiospecific one product forms where two are possible
If both ends have similar substitution, then not regiospecific

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Mechanistic Source of Regiospecificity in

Addition Reactions

If addition involves a
carbocation intermediate
and there are two
possible ways to add
the route producing the
more alkyl substituted
cationic center is lower
in energy
alkyl groups stabilize
carbocation

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Mechanism of Electrophilic Addition:

Rearrangements of Carbocations

Carbocations undergo
structural rearrangements
following set patterns
1,2-H and 1,2-alkyl shifts
occur
Goes to give more stable
carbocation
Can go through less stable
ions as intermediates

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2. Addition of Water to Alkenes

Hydration of an alkene is the addition of H-OH to to give

an alcohol
Acid catalysts are used in high temperature industrial
processes: ethylene is converted to ethanol

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3. Addition of Sulfuric acid to Alkenes

3
3
3
.

2
+

4
2

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4. Addition of HX to alkenes with peroxides

Free-radical reaction
Anti-Markovnikov addition

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5. Reduction of Alkenes: Hydrogenation

Addition of H-H across C=C

Reduction in general is addition of H2 or its equivalent
Requires Pt or Pd as powders on carbon and H2
Hydrogen is first adsorbed on catalyst
Reaction is heterogeneous (process is not in solution)

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5. Hydrogenation of alkenes

Syn-addition

Examples

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Hydrogen Addition- Selectivity

Selective for C=C. No reaction with C=O, C=N

Polyunsaturated liquid oils become solids
If one side is blocked, hydrogen adds to other

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Mechanism of Catalytic Hydrogenation

Heterogeneous reaction between phases

Addition of H-H is syn

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6. Addition of Halogens to Alkenes

Bromine and chlorine add to alkenes to give 1,2-dihaldes,

an industrially important process
F2 is too reactive and I2 does not add
Cl2 reacts as Cl+ Cl Br2 is similar

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Addition of Br2 to Cyclopentene

Addition is exclusively trans (anti-addition)

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Mechanism of Bromine Addition

Br+ adds to an alkene producing a cyclic ion

Bromonium ion, bromine shares charge with carbon
Gives trans addition

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Bromonium Ion Mechanism

Electrophilic addition of
bromine to give a cation is
followed by cyclization to
give a bromonium ion
This bromoniun ion is a
reactive electrophile and
bromide ion is a good
nucleophile

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7. Halohydrin Formation

This is formally the addition of HO-X to an alkene (with

+OH as the electrophile) to give a 1,2-halo alcohol, called
a halohydrin
The actual reagent is the dihalogen (Br2 or Cl2 in water in
an organic solvent)

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Mechanism of Formation of a Bromohydrin

Br2 forms bromonium ion, then water adds

+
Orientation toward stable C species
Aromatic rings do not react

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An Alternative to Bromine

Bromine is a difficult reagent to use for this reaction

N-Bromosuccinimide (NBS) produces bromine in organic
solvents and is a safer source

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8. Addition of Radicals to Alkenes: Polymers

A polymer is a very large molecule consisting of

repeating units of simpler molecules, formed by
polymerization
Alkenes react with radical catalysts to undergo radical
polymerization
Ethylene is polymerized to poyethylene, for example

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8A. Free Radical Polymerization of Alkenes

Alkenes combine many times to give polymer

Reactivity induced by formation of free radicals

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Free Radical Polymerization: Initiation

Initiation - a few radicals are generated by the reaction of a

molecule that readily forms radicals from a nonradical
molecule
A bond is broken homolytically

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Polymerization: Propagation

Radical from intiation adds to alkene to generate

alkene derived radical
This radical adds to another alkene, and so on many
times

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Polymerization: Termination

Chain propagation ends when two radical chains combine

Not controlled specifically but affected by reactivity and
concentration

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Other Polymers

Other alkenes give other common polymers

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8B. Cationic Polymerization

Vinyl monomers react with Brnsted or Lewis acid to

produce a reactive carbocation that adds to alkenes
and propagates via lengthening carbocations

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9. Hydroxylation using OsO4

Hydroxylation adds OH to each end of C=C

Catalyzed by osmium tetroxide
Stereochemistry of addition is syn
Product is a 1,2-dialcohol or diol (also called a glycol)

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Osmium Tetroxide Catalyzed Formation of

Diols

Hydroxylation - converts to syn-diol

Osmium tetroxide, then sodium bisulfate
Via cyclic osmate di-ester

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Hydroxylation using KMnO4

4
2

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10. Oxymercuration Intermediates

For laboratory-scale hydration of an alkene

Use mercuric acetate in THF followed by sodium
borohydride
Markovnikov orientation
via mercurinium ion

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11. Hydroboration-Oxidation

Herbert Brown (HB) invented hydroboration (HB)

Borane (BH3) is electron deficient is a Lewis acid
Borane adds to an alkene to give an organoborane

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BH3 Is a Lewis Acid

Six electrons in outer shell

Coordinates to oxygen electron pairs in ethers

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Hydroboration-Oxidation Forms an
Alcohol from an Alkene

Addition of H-BH2 (from BH3-THF complex) to three

alkenes gives a trialkylborane
Oxidation with alkaline hydrogen peroxide in water
produces the alcohol derived from the alkene

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Orientation in Hydration via 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 (opposite of anti addition)

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Mechanism of Hydroboration

Borane is a Lewis acid

Alkene is Lewis base
Transition state involves anionic
development on B
The components of BH3 are
across C=C

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Hydroboration: Orientation in Addition Step

Addition in least crowded orientation, syn

Addition also is via most stable carbocation

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Hydroboration, Electronic Effects Give NonMarkovnikov

More stable carbocation is also consistent with steric

preferences

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Hydroboration - Oxygen Insertion Step

H2O2, OH- inserts OH in place of B

Retains syn orientation

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12. Addition of Carbenes to Alkenes

The carbene functional group is half of an alkene

Carbenes are electrically neutral with six electrons in the
outer shell
They symmetrically across double bonds to form
cyclopropanes

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Formation of Dichlorocarbene

Base removes proton

from chloroform
Stabilized carbanion
remains
Unimolecular Elimination
of Cl- gives electron
deficient species,
dichlorocarbene

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Reaction of Dichlorocarbene

Addition of dichlorocarbene is stereospecific cis

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Simmons-Smith Reaction

Equivalent of addition of CH2:

Reaction of diiodomethane with zinc-copper alloy
produces a carbenoid species
Forms cyclopropanes by cycloaddition

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B. Cleavage reactions of alkenes

1. Alkene Cleavage: Ozone

Ozone, O3, adds to alkenes to form molozonide

Reduce molozonide to obtain ketones and/or aldehydes

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Examples of Ozonolysis of Alkenes

Used in determination of structure of an unknown alkene

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2. Permangante Oxidation of Alkenes

Oxidizing reagents other than ozone also cleave alkenes

Potassium permanganate (KMnO4) can produce
carboxylic acids and carbon dioxide if Hs are present on
C=C

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3. Cleavage of 1,2-diols

Reaction of a 1,2-diol with periodic (per-iodic) acid, HIO4 ,

cleaves the diol into two carbonyl compinds
Sequence of diol formation with OsO4 followed by diol
cleavage is a good alternative to ozonolysis

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Mechanism of Periodic Acid Oxidation

Via cyclic periodate intermediate

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4. Epoxidation Using a Peroxyacid

Treat an alkene with a peroxyacid.

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4. Epoxidation Using a Peroxyacid

The peroxyacid epoxidation is very selective. Double

bonds that are more electron-rich react faster, and syn
stereochemistry is always abserved.

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Dienes: Reactions and Synthesis

Types of Dienes

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Preparations of 1,3-Butadienes

1. Acid-catalyzed dehydration of diols

+

3
3

3
3

2. Pyrolysis of alkenes

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Preparations of 1,3-Butadienes

3. Dimerization of acetylene

4. Others

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Preparations of 1,3- and 1,4-Butadienes

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Reactions of dienes

1. Addition reaction of H2 to dienes

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Reactions of dienes

2. Addition reaction of HX to dienes

Example

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Reactions of dienes

3. Addition reaction of X2 to dienes

Cl2

Cl

CCl4
1,2-addition

1,4-addition

Cl

Cl

Cl

Cl
Cl2

CCl4
Cl

Cl

Cl
Cl

1,2,3,4-Tetrachlorobutene
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Reactions of dienes

4. Diels-Alder reaction

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