19-Oct-17

ALKENES AND CYCLOALKENES

• Preparation. β-Elimination reactions (E1 and E2),
Zaitsev rule, Hofmann rule, examples.
• Properties – reactions of the electrophilic (AE), and
radical (AR) addition; Markovnikov and anti-
Markovnikov rule, examples.
• Oxidation of alkenes. Polymerization of alkenes.

Alkenes are hydrocarbons that contain a

carbon–carbon double bond.

A carbon–carbon double bond is both an important

structural unit and an important functional group in
organic chemistry.

The double bond is the site of most of the chemical

reactions that alkenes undergo.

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STRUCTURE AND BONDING IN ALKENES

All six atoms are coplanar. The carbon–carbon bond is a double bond made up
of the s component and the p component.
The p orbitals of two sp2 hybridized carbons overlap to produce a p bond.

ALKENE NOMENCLATURE

The longest continuous chain that includes the double bond forms the base name
of the alkene, and the chain is numbered in the direction that gives the doubly
bonded carbons their lower numbers.

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ALKENE NOMENCLATURE

Hydroxyl groups, however, outrank the double bond. Compounds that contain
both a double bond and a hydroxyl group use the combined suffix -en + -ol to
signify that both functional groups are present.

Name each of the following using IUPAC nomenclature:

2,3-dimethyl-2-butene
4-chloro-1-pentene

2-methyl-2-hexene
4-penten-2-ol

ALKENE NOMENCLATURE
Cycloalkenes

Isomerism

cis-2-Butene and trans-2-butene are stereoisomers, and the terms “cis” and
“trans” specify the configuration of the double bond.

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PREPARATION OF ALKENES:
ELIMINATION REACTIONS

(β) elimination reactions, or 1,2 eliminations

High-temperature dehydrogenation of ethane and propane.

Both reactions involve b elimination of H2.

DEHYDRATION OF ALCOHOLS

In the dehydration of alcohols, the H and OH are lost from adjacent carbons.
An acid catalyst is necessary.

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Secondary alcohols undergo elimination at lower temperatures than primary alcohols.

Tertiary alcohols at lower temperatures than secondary alcohols.

REGIOSELECTIVITY IN ALCOHOLE DEHYDRATION:

THE ZAITSEV RULE

In alcohols such as 2-methyl-2-butanole dehydration can occur in two different

directions to give alkenes that are constitutional isomers. Here, a double bond
can be generated between C-1 and C-2 or between C-2 and C-3.

Elimination occurs in the direction that leads to the double bond between C-2
and C-3 (major product) more than between C-2 and C-1 (minor product).

Reactions that can proceed in more than one direction, but in which one
direction is preferred, are said to be regioselective.

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In 1875, Alexander Zaitsev of the University of Kazan (Russia) set forth a

generalization describing the regioselectivity b-eliminations.
Zaitsev’s rule stated that the alkene formed in greatest amount is the one
that corresponds to removal of the hydrogen from the carbon having the
fewest hydrogens.

β elimination reactions of alcohols yield the most

highly substituted alkene as the major product

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DEHYDROHALOGENATION OF ALKYL HALIDES

Dehydrohalogenation is the loss of a hydrogen and a halogen from an alkyl halide.
It is one of the most useful methods for preparing alkenes by b elimination.

The reaction is carried out in the presence of a strong base, such as sodium
ethoxide (NaOCH2CH3) in ethyl alcohol as solvent.

Potassium hydroxide in ethyl alcohol is another base–solvent combination often

employed in the dehydrohalogenation of alkyl halides. Potassium tert-butoxide
[KOC(CH3)3] is the preferred base when the alkyl halide is primary.

The regioselectivity of dehydrohalogenation of alkyl halides follows the Zaitsev rule;

β elimination predominates in the direction that leads to the more highly substituted
alkene.

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MECHANISM OF THE DEHYDROHALOGENATION OF ALKYL HALIDES:

THE E2 MECHANISM
Proposed in the 1920s by Sir Christopher Ingold. Based on two main facts:

1. The reaction exhibits second-order kinetics; it is first-order in alkyl halide

and first-order in base.
Rate = k[alkyl halide][base]
Doubling the concentration of either the alkyl halide or the base doubles the reaction rate.
Doubling the concentration of both reactants increases the rate by a factor of 4.

2. The rate of elimination depends on the halogen, the reactivity of alkyl

halides increasing with decreasing strength of the carbon–halogen bond.

E2 is standing for elimination bimolecular

In the E2 mechanism the three key elements

1. C-H bond breaking

2. C=C p bond formation

3. C-X bond breaking

are all taking place at the same transition state. The carbon–hydrogen and
carbon–halogen bonds are in the process of being broken, the base is becoming
bonded to the hydrogen, a p bond is being formed, and the hybridization of
carbon is changing from sp3 to sp2.

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THE E1 MECHANISM

Typically, elimination by the E1 mechanism is observed only for tertiary and some
secondary alkyl halides, and then only when the base is weak or in low
concentration.
E1 = elimination unimolecular

1. It exhibits first order kinetics. Rate = k[alkyl halide]

2. The reactivity order parallels the ease of carbocation formation.

1. rate-determining ionization of
the alkyl halide to a carbocation

2. deprotonation
of the carbocation

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THE E1 MECHANISM

REACTIONS OF ALKENES: ADDITION REACTIONS

HYDROGENATION OF ALKENES

Hydrogenation is the addition of H2 to a multiple bond.

Hydrogenation of alkenes yields alkanes.

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ELECTROPHILIC ADDITION OF HYDROGEN HALIDES

TO ALKENES

In many addition reactions the attacking reagent, unlike H2, is a polar molecule.
Hydrogen halides are among the simplest examples of polar substances that add to
alkenes.

The reactivity of the hydrogen halides reflects their ability to donate a proton. Hydrogen iodide
is the strongest acid of the hydrogen halides and reacts with alkenes at the fastest rate.

It is called electrophilic addition because the reaction is triggered by the

attack of an electrophile (an acid) on the p electrons of the double bond. Using
the two p electrons to form a bond to an electrophile generates a carbocation
as a reactive intermediate; normally this is the rate-determining step.

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REGIOSELECTIVITY:
MARKOVNIKOV’S RULE

Markovnikov’s rule states that when an unsymmetrically substituted alkene reacts

with a hydrogen halide, the hydrogen adds to the carbon that has the greater
number of hydrogen substituents, and the halogen adds to the carbon having
fewer hydrogen substituents.

REGIOSELECTIVITY:
MARKOVNIKOV’S RULE

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MECHANISTIC BASIS FOR MARKOVNIKOV’S RULE

FREE-RADICAL ADDITION OF
HYDROGEN BROMIDE TO ALKENES

anti-Markovnikov addition
(peroxide effect)

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Д-р Георги Ставраков

MECHANISM ФАРМАЦЕВТИЧЕН ФАКУЛТЕТ
МУ – СОФИЯ

ADDITION OF SULFURIC ACID TO ALKENES

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ACID-CATALYZED HYDRATION OF ALKENES

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HYDROBORATION–OXIDATION OF ALKENES

HYDROBORATION
Hydroboration is a reaction in which a boron hydride, a compound of the type R2BH, adds to a carbon–
carbon bond. A new carbon–hydrogen bond and a carbon–boron bond result.

OXIDATION
Following hydroboration, the organoborane is oxidized by treatment with hydrogen peroxide in aqueous
base. This is the oxidation stage of the sequence; hydrogen peroxide is the oxidizing agent, and the
organoborane is converted to an alcohol.

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ADDITION OF HALOGENS TO ALKENES

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CONVERSION OF ALKENES TO VICINAL HALOHYDRINS

EPOXIDATION OF ALKENES

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EPOXIDATION OF ALKENES

OZONOLYSIS OF ALKENES

Ozone (O3) is the triatomic form of oxygen. It is a neutral but polar molecule that
can be represented as a hybrid of its two most stable Lewis structures.

Ozone is a powerful electrophile and undergoes a remarkable reaction with

alkenes in which both the s and p components of the carbon–carbon double
bond are cleaved to give a product referred to as an ozonide.

Ozonides undergo hydrolysis in water, giving carbonyl compounds.

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OZONOLYSIS

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POLYMERIZATION

PE
Ethylene Polyethylene

PP
Propene Polypropylene

PS

Styrene Polystyrene

PVC
Vinyl chloride Poly(vinyl chloride)

POLYMERIZATION

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POLYMERIZATION

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