Addition To Insaturated Bonds

Introduction to Organic Chemistry Prof.
ngelo de Ftima UFMG/Brazil
Electrophilic addition to alkenes and alkynes
Chapters 7 & 8 Chapter 20

Introduction to Organic Chemistry Prof. ngelo de Ftima UFMG/Brazil
Alkenes are hydrocarbons whose molecules contain the carboncarbon double bond.
Hydrocarbons whose molecules contain the carboncarbon triple bond are called alkynes.
The (E)-(Z) System for Designating Alkene Diastereomers
A system that works in all cases is based on the priorities of groups in the Cahn-Ingold-Prelog convention. This
system, called the (E)-(Z) system, applies to alkene diastereomers of all types.
Relative Stabilities of Alkenes
Cis and trans isomers of alkenes do not have the same stability.
Strain caused by crowding of two alkyl groups on the same side of a double bond makes cis isomers generally less
stable than trans isomers.
Relative Stabilities of Alkenes
Heat of Reaction
The addition of hydrogen to an alkene (hydrogenation) is an exothermic reaction; the enthalpy change involved is
called the heat of reaction or, in this specific case, the heat of hydrogenation.
Overall Relative Stabilities of Alkenes
Studies of numerous alkenes reveal a pattern of stabilities that is related to the number of alkyl groups
attached to the carbon atoms of the double bond.
The greater the number of attached alkyl groups (i.e., the more highly substituted the carbon atoms of
the double bond), the greater is the alkenes stability.
Cycloalkenes
The rings of cycloalkenes

containing five carbon
atoms or fewer exist only
in the cis form.
trans-Cyclohexene might resemble the structure shown. There is

evidence that it can be formed as a very reactive short-lived
intermediate in some chemical reactions, but it is not isolable as
a stable molecule.
trans-Cycloheptene has been observed spectroscopically, but it is

a substance with a very short lifetime and has not been isolated.
trans-Cyclooctene has been isolated, however. Here the ring is

large enough to accommodate the geometry required by a trans
double bond and still be stable at room temperature.
trans-Cyclooctene is chiral and exists as a pair of enantiomers.

You may wish to verify this using handheld models.
Synthesis of Alkenes via Elimination Reactions

Dehydrohalogenation of Alkyl Halides:
The best reaction conditions to use when synthesizing an alkene by dehydrohalogenation are those that promote an
E2 mechanism.
Reaction conditions that favor elimination by an E1 mechanism should be avoided because the results can be too
variable. The carbocation intermediate that accompanies an E1 reaction can undergo rearrangement of the carbon
skeleton and it can also undergo substitution by an SN1 mechanism, which competes strongly with formation of
products by an E1 path.
Dehydrohalogenation of Alkyl Halides: How to Favor an E2 Mechanism?
1. Use a secondary or tertiary alkyl halide if possible.

Why: Because steric hindrance in the substrate will inhibit substitution.
2. When a synthesis must begin with a primary alkyl halide, use a bulky base.
Why: Because the steric bulk of the base will inhibit substitution.
3. Use a high concentration of a strong and nonpolarizable base such as an alkoxide.

Why: Because a weak and polarizable base would not drive the reaction toward a bimolecular reaction, thereby
allowing unimolecular processes (such as SN1 or E1 reactions) to compete.
4. Sodium ethoxide in ethanol (EtONa/EtOH) and potassium tert-butoxide in tertbutyl alcohol (t-BuOK/t-
BuOH) are bases typically used to promote E2 reactions.
Why: Because they meet criterion 3 above.
5. Use elevated temperature because heat generally favors elimination over substitution.
Why: Because elimination reactions are entropically favored over substitution reactions (because the products
are greater in number than the reactants).
Dehydrohalogenation of Alkyl Halides: Zaitsevs Rule: Formation of the More Substituted Alkene Is Favored with a
Small Base.
Dehydrohalogenations where only a single elimination product was possible!!!

Small Base.
Dehydrohalogenation of many alkyl halides, however, yields more than one product.
Small Base.
Dehydrohalogenation of many alkyl halides, however, yields more than one product.
Small Base.
If we use a small base such as ethoxide or hydroxide, the major product of the reaction will be the more highly
substituted alkene (which is also the more stable alkene).
Whenever an elimination occurs to give the more stable, more highly substituted alkene, chemists say that the
elimination follows the Zaitsev rule, named for the nineteenth-century Russian chemist A. N. Zaitsev (18411910) who
formulated it. (Zaitsevs name is also transliterated as Zaitzev, Saytzeff, Saytseff, or Saytzev.)
Formation of the Less Substituted Alkene Using a Bulky Base
Carrying out dehydrohalogenations with a bulky base such as potassium tert-butoxide (t-BuOK) in tert-butyl
alcohol (t-BuOH) favors the formation of the less substituted alkene:
When an elimination yields the less substituted alkene, we say that it follows the Hofmann rule.
The Hofmann Elimination
All of the eliminations that we have described so far have involved electrically neutral substrates. However,
eliminations are known in which the substrate bears a positive charge. One of the most important of these is
the E2-type elimination that takes place when a quaternary ammonium hydroxide is heated. The products are
an alkene, water, and a tertiary amine:
Although most eliminations involving neutral substrates tend to

follow the Zaitsev rule, eliminations with charged substrates
This reaction was tend to follow what is called the Hofmann rule and yield
discovered in 1851 by mainly the least substituted alkene.
August W. von Hofmann
and has since come to
bear his name.
Quaternary ammonium hydroxides can be prepared from quaternary ammonium halides in aqueous solution
through the use of silver oxide or an ion exchange resin:
We can see an example of this behavior if we compare the following reactions:

The Stereochemistry of E2 Reactions: The Orientation of Groups in the Transition State
The five atoms involved in the transition state of an E2 reaction (including the base) must lie in the same plane.
The anti coplanar conformation is the preferred transition state geometry. The syn coplanar transition state
occurs only with rigid molecules that are unable to assume the anti arrangement.
Acid-Catalyzed Dehydration of Alcohols
Most alcohols undergo dehydration (lose a molecule of water) to form an alkene when heated with a strong acid.
1. The temperature and concentration of acid required to dehydrate an alcohol depend on the structure of the
alcohol substrate.
(a) Primary alcohols are the most difficult to dehydrate. Dehydration of ethanol, for example, requires concentrated
sulfuric acid and a temperature of 180C:
(b) Secondary alcohols usually dehydrate under milder conditions. Cyclohexanol, for example, dehydrates in 85%
phosphoric acid at 165170C:
(c) Tertiary alcohols are usually so easily dehydrated that extremely mild conditions can be used. tert-Butyl alcohol,
for example, dehydrates in 20% aqueous sulfuric acid at a temperature of 85C:
Thus, overall, the relative ease with which alcohols undergo dehydration is in the following order:
Most alcohols undergo dehydration (lose a molecule of water) to form an alkene when heated with a strong acid.
2. Some primary and secondary alcohols also undergo rearrangements of their carbon skeletons during
dehydration. Such a rearrangement occurs in the dehydration of 3,3-dimethyl-2-butanol:
Mechanism for Dehydration of Secondary and Tertiary Alcohols: An E1 Reaction




A Mechanism for Dehydration of Primary Alcohols: An E2 Reaction
Dehydration of primary alcohols apparently proceeds through an E2 mechanism because the primary carbocation
required for dehydration by an E1 mechanism is relatively unstable.
A Mechanism for Dehydration of Primary Alcohols: An E2 Reaction

Rearrangements during Dehydration of Secondary Alcohols


Now the
rearrangement
occurs.
Now the
rearrangement
occurs.
The conditions for the reaction

(heat and acid) allow equilibrium
to be achieved between the two
forms of the alkene, and the
more stable alkene is the major
product because it has lower
potential energy. Such a reaction
is said to be under equilibrium or
thermodynamic control.
Path (b) leads to the highly stable

tetrasubstituted alkene and this is
the path followed by most of the
carbocations.
Path (a), on the other hand, leads

to a less stable, disubstituted
The more favored product is alkene, and because its potential
dictated by the stability of the energy is higher, it is the minor
alkene being formed. product of the reaction.
Formation of the more stable alkene is the general rule in acid-catalyzed dehydration of alcohols (Zaitsevs rule).
Studies of many reactions involving carbocations show that rearrangements like those just described are general
phenomena. They occur almost invariably when the migration of an alkanide ion or hydride ion can lead to a more
stable carbocation.
The following are examples:

The Acidity of Terminal Alkynes

Synthesis of Alkynes by Elimination Reactions
Alkynes can be synthesized from alkenes via compounds called vicinal dihalides.
Synthesis of Alkynes by Elimination Reactions
Geminal dihalides can also be converted to alkynes by dehydrohalogenation.

Electrophilic addition to alkenes and alkynes
Chapters 7 & 8 Chapter 20

Hydrogenation: The Function of the Catalyst
Hydrogenation of an alkene is an exothermic reaction (H 120 kJ mol-1):


Hydrogenation of Alkynes.
Depending on the conditions and the catalyst employed, one or two molar equivalents of hydrogen will add to a
carbon-carbon triple bond. When a platinum catalyst is used, the alkyne generally reacts with two molar
equivalents of hydrogen to give an alkane:
However, hydrogenation of an alkyne to an alkene can be accomplished through the use of special catalysts or
reagents. Moreover, these special methods allow the preparation of either (E)- or (Z)-alkenes from disubstituted
alkynes.
Hydrogenation of Alkynes: Syn Addition of Hydrogen: Synthesis of Z-Alkenes.
Hydrogenation of alkynes in the presence of P-2 catalyst causes syn addition of hydrogen. The alkene formed
from an internal alkyne has the (Z).
This special catalyst is known as Lindlars catalyst:

Hydrogenation of Alkynes: Syn Addition of Hydrogen: Synthesis of Z-Alkenes.

Hydrogenation of Alkynes: Anti Addition of Hydrogen: Synthesis of E-Alkenes.
Anti addition of hydrogen to the triple bond of alkynes occurs when they are treated with lithium or sodium
metal in ammonia or ethylamine at low temperatures.
This reaction, called a dissolving metal reduction, takes place in solution and produces an (E)-alkene. The
mechanism involves radicals, which are molecules that have
unpaired electrons.
Addition Reactions of Alkenes: More examples!

How to Understand Additions to Alkenes
An addition reaction results in the conversion of one p bond and one s bond into two s bonds. The result of this
change is usually energetically favorable. The energy released in making two s bonds exceeds that needed to break
one s bond and one p bond (because p bonds are weaker), and, therefore, addition reactions are usually
exothermic:
The electrons of the p bond are exposed. Because the p bond results from overlapping p orbitals, the p electrons
lie above and below the plane of the double bond:
Electrophilic Addition:
Electrons in the p bond of alkenes react with electrophiles;
Electrophiles are electron-seeking reagents. They have the property of being electrophilic.
Electrophilic Addition of Hydrogen Halides to Alkenes: Mechanism and Markovnikovs Rule
Hydrogen halides (HI, HBr, HCl, and HF) add to the double bond of alkenes:
The order of reactivity of the hydrogen halides in alkene addition is HI > HBr > HCl > HF.
Consideration of many examples like this led the Russian chemist Vladimir Markovnikov in 1870 to formulate what is
now known as Markovnikovs rule.
One way to state Markovnikovs rule is to say that in the addition of HX to an alkene, the hydrogen atom adds to the
carbon atom of the double bond that already has the greater number of hydrogen atoms.*
*In his original publication, Markovnikov described the rule in terms of the point of attachment of the halogen atom, stating that if an unsymmetrical
alkene combines with a hydrogen halide, the halide ion adds to the carbon atom with the fewer hydrogen atoms.


Theoretical Explanation of Markovnikovs Rule

Theoretical Explanation of Markovnikovs Rule
The more stable carbocation predominates because it is formed faster.

Modern Statement of Markovnikovs Rule
In the ionic addition of an unsymmetrical reagent to a double bond, the positive portion of the adding reagent
attaches itself to a carbon atom of the double bond so as to yield the more stable carbocation as an intermediate.
Regioselective Reactions
Chemists describe reactions like the Markovnikov additions of hydrogen halides to alkenes as being regioselective.
Regio comes from the Latin word regionem meaning direction.
When a reaction that can potentially yield two or more constitutional isomers actually produces only one (or a
predominance of one), the reaction is said to be regioselective.
An Exception to Markovnikovs Rule
When alkenes are treated with HBr in the presence of peroxides, an anti-Markovnikov addition occurs in the sense that
the hydrogen atom becomes attached to the carbon atom with the fewer hydrogen atoms.
With propene, for example, the addition takes place as follows:
This anti-Markovnikov addition occurs only when HBr is used in the presence of peroxides and does not occur
significantly with HF, HCl, and HI even when peroxides are present.
Stereochemistry of the Ionic Addition to an Alkene

Addition of Sulfuric Acid to Alkenes
When alkenes are treated with cold concentrated sulfuric acid, they dissolve because they react by electrophilic
addition to form alkyl hydrogen sulfates.
The addition of sulfuric acid is

also regioselective, and it follows
Markovnikovs rule. Propene, for
example, reacts to yield isopropyl
hydrogen sulfate rather than
propyl hydrogen sulfate:
Alcohols from Alkyl Hydrogen Sulfates

Addition of Water to Alkenes: Acid-Catalyzed Hydration
These reactions, too, are usually regioselective, and the addition

of water to the double bond follows Markovnikovs rule.
Rearrangements: One complication associated with alkene hydrations is the occurrence of rearrangements.
Alcohols from Alkenes through Oxymercuration-Demercuration: Markovnikov Addition
Alkenes react with mercuric acetate in a mixture of tetrahydrofuran (THF) and water to produce
(hydroxyalkyl)mercury compounds. These (hydroxyalkyl)mercury compounds can be reduced to alcohols with
sodium borohydride.
In the first step, oxymercuration, water and

mercuric acetate add to the double bond.
In the second step, demercuration, sodium borohydride reduces the

acetoxymercury group and replaces it with hydrogen.
Regioselectivity of Oxymercuration-Demercuration
In oxymercuration-demercuration, the net orientation of the addition of the elements of water, H and
OH, is in accordance with Markovnikovs rule. The H becomes attached to the carbon atom of the
double bond with the greater number of hydrogen atoms.
Rearrangements Seldom Occur in Oxymercuration-Demercuration
Rearrangements of the carbon skeleton seldom occur in oxymercuration-demercuration.
Central to this mechanism is an electrophilic attack by the

mercury species, +HgOAc, at the less substituted carbon of the
double bond (i.e., at the carbon atom that bears the greater
number of hydrogen atoms), and the formation of a bridged
intermediate.
Write the mechanism for the demercuration reaction!!!
Alcohols from Alkenes through Hydroboration-Oxidation: Anti-Markovnikov Syn Hydration
Anti-Markovnikov hydration of a double bond can be achieved through the use of diborane (B2H6) or a
solution of borane in tetrahydrofuran (BH3:THF).
Hydroboration-oxidation takes place with syn stereochemistry, as well as anti-Markovnikov regiochemistry.

Mechanism of Hydroboration
Mechanism of Hydroboration
Stereochemistry of Hydroboration
Oxidation and Hydrolysis of Alkylboranes
The oxidation and hydrolysis steps take place with retention of

configuration at the carbon initially bearing boron and
ultimately bearing the hydroxyl group.
Oxidation and Hydrolysis of Alkylboranes: Mechanism

Regiochemistry and Stereochemistry of Alkylborane Oxidation and Hydrolysis
Hydroborationoxidation reactions are regioselective; the net result of hydroboration-oxidation is anti-

Markovnikov addition of water to an alkene.
As a consequence, hydroboration-oxidation gives us a method for the preparation of alcohols that cannot
normally be obtained through the acid-catalyzed hydration of alkenes or by oxymercuration-demercuration.
Hydroboration-oxidation reactions are stereospecific; the net addition of H and OH is syn, and if chirality
centers are formed, their configuration depends on the stereochemistry of the starting alkene.
Electrophilic Addition of Bromine and Chlorine to Alkenes
Examples of the addition of halogens to a double bond are the following:

Stereospecific Reactions
A reaction is stereospecific when a particular stereoisomeric form of the starting material reacts by a
mechanism that gives a specific stereoisomeric form of the product.
Halohydrin Formation
When the halogenation of an alkene is carried out in aqueous solution, rather than in
a non-nucleophilic solvent, the major product is a halohydrin (also called a halo
alcohol) instead of a vic-dihalide.
Oxidation of Alkenes: Syn 1,2-Dihydroxylation
Osmium tetroxide is widely used to synthesize 1,2-diols (the products of 1,2-dihydroxylation, sometimes also called
glycols). Potassium permanganate can also be used, although because it is a stronger oxidizing agent it is prone to
cleave the diol through further oxidation.
Mechanism for Syn Dihydroxylation of Alkenes
The mechanism for the formation of a 1,2-diol by osmium

tetroxide involves a cyclic intermediate that results in syn
addition of the oxygen atoms (see below).
Oxidative Cleavage of Alkenes
Cleavage with Hot Basic Potassium Permanganate
Treatment with hot basic potassium permanganate oxidatively cleaves the double bond of an alkene.
Cleavage with Ozone
The most useful method for cleaving alkenes is to use ozone (O3). The overall process (above) results in alkene
cleavage at the double bond, with each carbon of the double bond becoming doubly bonded to an oxygen atom.
Electrophilic Addition of Bromine and Chlorine to Alkynes
Alkynes show the same kind of addition reactions with chlorine and bromine that alkenes do.
With alkynes the addition may occur once or twice, depending on the number of molar equivalents of
halogen we employ:
Addition of one molar equivalent of chlorine or bromine to an alkyne generally results in

anti addition and yields a trans-dihaloalkene.
Addition of Hydrogen Halides to Alkynes
Alkynes react with one molar equivalent of hydrogen chloride or hydrogen bromide to
form haloalkenes, and with two molar equivalents to form geminal dihalides.
Both a additions re regioselective and follow Markovnikovs rule:
Example:
anti-Markovnikov addition of hydrogen bromide to alkynes occurs when peroxides are present
in the reaction mixture. These reactions take place through a free-radical mechanism.
Oxidative Cleavage of Alkynes
Treating alkynes with ozone followed by acetic acid, or with

basic potassium permanganate followed by acid, leads to
cleavage at the carbon-carbon triple bond. The products are
carboxylic acids:

Addition To Insaturated Bonds

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Addition To Insaturated Bonds

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Introduction to Organic Chemistry Prof.

ngelo de Ftima UFMG/Brazil

Electrophilic addition to alkenes and alkynes

Chapters 7 & 8 Chapter 20

The (E)-(Z) System for Designating Alkene Diastereomers

Relative Stabilities of Alkenes

Relative Stabilities of Alkenes

Overall Relative Stabilities of Alkenes

The rings of cycloalkenes

trans-Cyclohexene might resemble the structure shown. There is

trans-Cycloheptene has been observed spectroscopically, but it is

trans-Cyclooctene has been isolated, however. Here the ring is

trans-Cyclooctene is chiral and exists as a pair of enantiomers.

Synthesis of Alkenes via Elimination Reactions

Dehydrohalogenation of Alkyl Halides:

Dehydrohalogenation of Alkyl Halides: How to Favor an E2 Mechanism?

1. Use a secondary or tertiary alkyl halide if possible.

3. Use a high concentration of a strong and nonpolarizable base such as an alkoxide.

Dehydrohalogenations where only a single elimination product was possible!!!

Formation of the Less Substituted Alkene Using a Bulky Base

The Hofmann Elimination

Although most eliminations involving neutral substrates tend to

The Hofmann Elimination

The Hofmann Elimination

We can see an example of this behavior if we compare the following reactions:

The Stereochemistry of E2 Reactions: The Orientation of Groups in the Transition State

Acid-Catalyzed Dehydration of Alcohols

Acid-Catalyzed Dehydration of Alcohols

Acid-Catalyzed Dehydration of Alcohols

Acid-Catalyzed Dehydration of Alcohols

Mechanism for Dehydration of Secondary and Tertiary Alcohols: An E1 Reaction

Mechanism for Dehydration of Secondary and Tertiary Alcohols: An E1 Reaction

Mechanism for Dehydration of Secondary and Tertiary Alcohols: An E1 Reaction

Mechanism for Dehydration of Secondary and Tertiary Alcohols: An E1 Reaction

A Mechanism for Dehydration of Primary Alcohols: An E2 Reaction

A Mechanism for Dehydration of Primary Alcohols: An E2 Reaction

Rearrangements during Dehydration of Secondary Alcohols

Rearrangements during Dehydration of Secondary Alcohols

Rearrangements during Dehydration of Secondary Alcohols

Rearrangements during Dehydration of Secondary Alcohols

Rearrangements during Dehydration of Secondary Alcohols

The conditions for the reaction

Path (b) leads to the highly stable

Path (a), on the other hand, leads

Rearrangements during Dehydration of Secondary Alcohols

The following are examples:

The Acidity of Terminal Alkynes

Synthesis of Alkynes by Elimination Reactions

Synthesis of Alkynes by Elimination Reactions

Geminal dihalides can also be converted to alkynes by dehydrohalogenation.

Electrophilic addition to alkenes and alkynes

Chapters 7 & 8 Chapter 20

Hydrogenation: The Function of the Catalyst

Hydrogenation of an alkene is an exothermic reaction (H 120 kJ mol-1):

Hydrogenation: The Function of the Catalyst

Hydrogenation: The Function of the Catalyst

Hydrogenation: The Function of the Catalyst

Hydrogenation of Alkynes: Syn Addition of Hydrogen: Synthesis of Z-Alkenes.

This special catalyst is known as Lindlars catalyst:

Hydrogenation: The Function of the Catalyst

Hydrogenation of Alkynes: Syn Addition of Hydrogen: Synthesis of Z-Alkenes.

Hydrogenation: The Function of the Catalyst

Hydrogenation of Alkynes: Anti Addition of Hydrogen: Synthesis of E-Alkenes.