CCB1013 Organic Chemistry

By Dr. Oh Pei Ching

Chapter 8: Alkenes and Alkynes II Addition Reactions

Alkenes and Alkynes II

CCB1013 Organic Chemistry

Learning Outcomes
By the end of this lecture, you should be able to:
Use curved arrow notation in addition mechanism Understand additions to alkenes and alkynes (hydrogen halides, sulfuric acid, water and halogens) Identify proton donors and acceptors in proton transfer steps Understand stereochemistry, regiochemistry, and conditions for use of a variety of reagents that add to alkenes and alkynes

CCB1013 Organic Chemistry

Introduction: Addition Reactions to Alkenes

Electrophilic

Nucleophilic

Example:

CCB1013 Organic Chemistry

Introduction: Addition Reactions to Alkenes

How to Understand Additions to Alkenes
An addition reaction results in the conversion of one

bond and one bond into two bonds. Generally, addition reactions are exothermic.

CCB1013 Organic Chemistry

Introduction: Addition Reactions to Alkenes

How to Understand Additions to Alkenes
Since bonds are formed from the overlapping of p orbitals, electron clouds are above and below the plane of the double bond. The electrons are loosely held and are a source of electron density (nucleophilic).

electron clouds

CCB1013 Organic Chemistry

Introduction: Addition Reactions to Alkenes

Electrophilic Addition
C=C and CC bonds are particularly susceptible to electrophilic reagents (electrophiles). Common electrophiles: H+, X+ (X = Cl, Br, I), Hg2+, etc. In addition reactions, the alkene changes from a nucleophile in the first step to an electrophile in the second.

Recall: Electrophiles can accept e Nucleophile can donate e

CCB1013 Organic Chemistry

Electrophilic Addition of Hydrogen Halides to Alkenes: Mechanism and Markovnikovs Rule

Hydrogen halides add to the double bond of alkenes:

Markovnikovs Rule: For symmetrical substrates, no problem for regiochemistry.

H C H C H H E E Nu H C H C H Nu E H C H Nu C H same H as H Nu E C H C H
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same H as H

E C H C H H

CCB1013 Organic Chemistry

Electrophilic Addition of Hydrogen Halides to Alkenes: Mechanism and Markovnikovs Rule

Markovnikovs Rule: But for unsymmetrical substrates, two regioisomers are possible.

H3C C H C

H H

Nu CH3

E C H C H Nu E CH3 C H Nu C H different H from CH3 H or CH3 C H

E C H Nu Nu E C H C H
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CCB1013 Organic Chemistry

Electrophilic Addition of Hydrogen Halides to Alkenes: Mechanism and Markovnikovs Rule

Markovnikovs Rule: Addition of HX to an alkene proceeds so that the hydrogen atom adds to the carbon that already has the most hydrogen atoms.

Example: Addition of HBr to propene occurs to give 2-bromopropane as the major product.

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Electrophilic Addition of Hydrogen Halides to Alkenes: Mechanism and Markovnikovs Rule

Mechanism for addition of hydrogen halide to alkene
Ratedetermining step

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Electrophilic Addition of Hydrogen Halides to Alkenes: Mechanism and Markovnikovs Rule

Free-energy diagram for addition of hydrogen halide to alkene The reaction has a highly endergonic first step (rate determining) and a highly exergonic second step.

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Electrophilic Addition of Hydrogen Halides to Alkenes: Mechanism and Markovnikovs Rule

Theoretical Explanation of Markovnikovs Rule: The product with the more stable carbocation intermediate predominates (because it is formed faster). The most stable carbocation is formed fastest because it has a lower G.
The transition state for the rate determining step (first step) resembles a carbocation and is stabilized by factors which stabilize carbocations.

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Electrophilic Addition of Hydrogen Halides to Alkenes: Mechanism and Markovnikovs Rule

Theoretical Explanation of Markovnikovs Rule: The product with the more stable carbocation intermediate predominates (because it is formed faster). The most stable carbocation is formed fastest because it has a lower G.
The transition state for the rate determining step (first step) resembles a carbocation and is stabilized by factors which stabilize carbocations.

G(2o) < G(1o) 2o carbocation forms faster

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Electrophilic Addition of Hydrogen Halides to Alkenes: Mechanism and Markovnikovs Rule

Mechanism for addition of HBr to 2-methylpropene
This reaction takes place

This reaction does not occur to any appreciable extent

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Electrophilic Addition of Hydrogen Halides to Alkenes: Mechanism and Markovnikovs Rule

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: A reaction that can potentially yield two or more constitutional isomers actually produces only one or a predominance of one isomer. Markovnikov additions of hydrogen halides to alkenes are regioselective.
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Electrophilic Addition of Hydrogen Halides to Alkenes: Mechanism and Markovnikovs Rule

Exception to Markovnikovs Rule:
AntiMarkovnikov Product

Anti-Markovnikov addition occurs when alkenes are treated with HBr in the presence of peroxides (ROOR). Addition occurs via a radical mechanism. This anti-Markovnikov addition does not take place with HI, HCl, and HF, even when peroxides are present.

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Stereochemistry of the Ionic Addition to an Alkene

Addition of HX to 1-hexene yields a chiral molecule. A racemic mixture is produced because the intermediate carbocation is achiral.
attack from top

X
H

X C CH3
racemate
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H C Bu C

H H

H Bu

CH2

Bu (S)-2-Halohexane (50%) H

1-Hexene donates a pair of electrons to the proton of HX to form an achiral carbocation.

achiral trigonal planar carbocation attack from bottom

H Bu C CH3
X X (R)-2-Halohexane (R)-2-Halohexane (50%) (50%)

CCB1013 Organic Chemistry

Addition of Sulfuric Acid to Alkenes

Addition of cold concentrated sulfuric acid to alkenes leads to alkyl hydrogen sulfates which are soluble in the acid. The addition follows Markovnikovs rule.

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Addition of Sulfuric Acid to Alkenes

Alcohols from Alkyl Hydrogen Sulfates: Alkyl hydrogen sulfates can be hydrolyzed by heating with water. The net result is Markovnikov addition of water to an alkene.

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Addition of Water to Alkenes: Acid-Catalyzed Hydration

The reaction of alkenes with dilute aqueous acid (e.g. dilute H2SO2 and H3PO4) leads to Markovnikov addition of water.

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Addition of Water to Alkenes: Acid-Catalyzed Hydration

Mechanism:

Ratedetermining step

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Addition of Water to Alkenes: Acid-Catalyzed Hydration

The hydration of alkenes and the dehydration of alcohols are simply reverse reactions of one other.
The reaction is governed by the position of all the equilibria. # Hydration is favored by addition of a small amount of acid and a large amount of water. # Dehydration is favored by concentrated acid with very little water present (removal of water produced also helps favor dehydration).
#

Rearrangements: One complication associated with alkene hydration is the occurrence of rearrangements, as carbocation formed initially may rearrange to a more stable one.
How to avoid rearrangement? Oxymercuration -demercuration

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Alcohols from Alkenes through OxymercurationDemercuration: Markovnikov Addition

Oxymercuration-demercuration procedure gives high yields of alcohols and avoids rearrangements.
OAc

Alkene

mercuric acetate

(hydroxyalkyl)mercury

Water and mercuric acetate add to the double bond

sodium borohydride

alcohol

Sodium borohydride reduces the acetoxymercury group and replaces it with hydrogen
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Alcohols from Alkenes through OxymercurationDemercuration: Markovnikov Addition

Oxymercurationdemercuration is also highly regioselective and follows Markovnikovs rule.

Specific Examples:

No rearrangement

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Alcohols from Alkenes through OxymercurationDemercuration: Markovnikov Addition

Mechanism of Oxymercuration
The mechanism involves formation of a bridged mercurinium ion.

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Alcohols from Alkenes through OxymercurationDemercuration: Markovnikov Addition

Mechanism of Oxymercuration
The mechanism involves formation of a bridged mercurinium ion.

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Alcohols from Alkenes through HydroborationOxidation: Anti-Markovnikov Syn Addition

Hydroboration-Oxidation:
The reaction leads to syn and anti-Markovnikov addition of water to alkenes.

Hydroboration: Synthesis of Alkylboranes

The elements of hydrogen and boron are added across the double bond.

In practice, a borane complex with the solvent tetrahydrofuran (THF) is often used.

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Alcohols from Alkenes through HydroborationOxidation: Anti-Markovnikov Syn Addition

Hydroboration: Mechanism
When terminal alkene (e.g. propene) is treated with solution containing BH3:THF, boron hydride adds successively to three molecules of alkene.

Boron becomes attached to the least substituted carbon of the double bond.
The bulky boron group can approach the least sterically hindered carbon more easily. This orientation also allows a + charge in the transition state to reside at the most substituted carbon. This orientation leads to anti-Markovnikov product. CCB1013 Organic Chemistry
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Alcohols from Alkenes through HydroborationOxidation: Anti-Markovnikov Syn Addition

Hydroboration: Mechanism
Boron becomes attached to the least substituted carbon of the double bond.

Boron attachment

The boron and hydride add with syn stereochemistry.

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Alcohols from Alkenes through HydroborationOxidation: Anti-Markovnikov Syn Addition

Oxidation and Hydrolysis of Alkylboranes
Oxidation and hydrolysis to the alcohol takes place with retention of stereochemistry at the carbon bonded to boron.

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Alcohols from Alkenes through HydroborationOxidation: Anti-Markovnikov Syn Addition

Oxidation of trialkylboranes: Mechanism

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Alcohols from Alkenes through HydroborationOxidation: Anti-Markovnikov Syn Addition

The hydroboration-oxidation of 1-methylcyclopentene gives the antiMarkovnikov product with syn addition of the elements of water.

Summary of Alkene Hydration Methods:

Acid-catalyzed hydrolysis: Markovnikov addition Oxymercuration-demercuration: Markovnikov addition Hydroboration-oxidation: anti-Markovnikov and syn addition
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Addition of Bromine and Chlorine to Alkenes

Addition produces vicinal dihalides. The addition of halogens is an anti addition to the double bond.

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Addition of Bromine and Chlorine to Alkenes

Bromine serve as a test for the presence of carbon-carbon multiple bonds. If bromine is added to an alkene (or alkyne), the red color of the bromine reagent disappears when an alkene (or alkyne) is present in excess.

Alkanes do not react appreciably with bromine or chlorine at room temperature in the dark.

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Addition of Bromine and Chlorine to Alkenes

Mechanism:
A bromonium ion intermediate results instead of the carbocation seen in other addition reactions.

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Addition of Bromine and Chlorine to Alkenes

Stereochemistry:
The net result is anti addition because of SN2 attack on the bromonium ion intermediate. When cyclopentene reacts the product is a racemic mixture of trans-1,2dibromocyclopentane enantiomers.

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Addition of Bromine and Chlorine to Alkenes

Stereospecific Reactions:
A reaction is stereospecific if a particular stereoisomeric form of the starting material reacts in such a way that it gives a specific stereoisomeric form of the product. Example: cis- and trans-2-butene give stereoisomeric products when halogenated. Halogenation of double bonds is stereospecific.
Reaction 1

Reaction 2

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Addition of Bromine and Chlorine to Alkenes

Halohydrin Formation:
If halogenation is carried out in aqueous solvent (not nucleophilic solvent such as CCl4), the water molecule can act as a nucleophile to open the halonium ion. The product is a halohydrin.

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Addition of Bromine and Chlorine to Alkenes

Halohydrin Formation Mechanism:

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Addition of Bromine and Chlorine to Alkenes

Halohydrin Formation:
In unsymmetrical alkenes, the bromonium ion will have some of its + charge density on the most substituted of the two carbons. The most substituted carbon can best accommodate + charge. The water nucleophile will tend to react at the carbon with the most + charge.

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Addition of Bromine and Chlorine to Alkynes

Addition of halogen to alkynes can occur once or twice depending on how many equivalents of the halogen are added. Addition of one equivalent usually proceeds to give the trans dihalide through anti addition.

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Addition of Hydrogen Halides to Alkynes

Addition of hydrogen halides occurs once or twice depending on how many molar equivalent of hydrogen halide are added. Both additions are Markovnikov and give gem-halides.

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Addition of Hydrogen Halides to Alkynes

HBr can be generated by reaction of acetyl bromide and alumina.

Anti-Markovnikov addition of HBr occurs in the presence of peroxide.

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