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7. Reactions of Alkenes
Read chapter 8 of Organic Chemistry, 7th Edition L. G. Wade, Jr.
2010, Prentice Hall

Bonding in Alkenes
Electrons in pi-bond are loosely held. The double bond reacts with an electrophilic species. Carbocations are intermediates in the reactions. These reactions are called electrophilic additions.
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Electrophilic Addition
Step 1: Pi electrons attack the electrophile.

Step 2: Nucleophile attacks the carbocation.

Electrophilic Addition Reactions

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Addition of HX to Alkenes
Step 1: Protonation of the double bond to form the most stable carbocation possible.

Step 2: Nucleophilic attack of the halide on the carbocation.

Markovnikovs Rule

Markovnikovs Rule: The proton adds to the carbon atom that already holds the greater number of hydrogens. Modified Markovnikovs Rule: In an electrophilic addition to the alkene, the electrophile adds in such a way that it generates the most stable intermediate. 6

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Free-Radical Addition of HBr

In the presence of peroxides, HBr adds to an alkene to form the anti-Markovnikov product. Peroxides produce free radicals. Only HBr has the right bond energy. The HCl bond is too strong, so it will add according to Markovnikovs rule, even in the presence of peroxide. The HI bond tends to break heterolytically to form ions, it too will add according to Markovnikovs rule.

Free-Radical Initiation
The peroxide bond breaks homolytically to form the first radical: Hydrogen is abstracted from HBr.

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Propagation Steps
Bromine adds to the double bond forming the most stable radical possible:
CH3 CH3 C CH CH3 + Br CH3 CH3 C CH Br tertiary radical (more stable) CH3

Hydrogen is abstracted from HBr:

Br H CH3 C H C

CH H 3
+ CH3 H Br

Br

H CH3 C H CH3
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CH H 3

C H

Br

anti-Markovnikov product

Hydration of Alkenes

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Regioselectivity of Hydration
CH3 CH3 C CH CH3 + H H O H CH3 CH3 C
o

CH CH3 H

3 , more stable

The protonation follows Markovnikovs rule: The hydrogen is added to the less substituted carbon in order to form the most stable carbocation.

CH3 CH3 C H 2o less stable, not formed

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CH CH3

Rearrangements
CH3 CH3 C CH CH3 CH2 50% H2SO4 CH3 CH3 C CH CH3 OH CH3

Rearrangement:
CH3 CH3 C CH CH3 CH3 2o, less stable CH3 CH3 C CH CH3 CH3 3o, more stable

H2O

CH3 CH3 C CH CH3 OH CH3 2,3-dimethyl-2-butanol (major product)

The carbocation can rearrange to produce a more stable carbocation.

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Problem 1
Show a reaction to convert 1-methylcyclohexene to 1-bromo-1-methylcyclohexane.
Solution

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Problem 2
Show a reaction series to convert 1-methylcyclohexanol to 1-bromo-2-methylcyclohexane.
Solution

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OxymercurationDemercuration Reaction

Markovnikov addition of water to the double bond. No rearrangements. Two-step process.

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Mechanism of Oxymercuration

Mercuric acetate cation reacts with the double bond to form mercurinium ion Water adds to the more substituted carbon of the mercurinium ion to form the Markovnikov product. Water approaches the mercurinium ion from the side opposite 16 the ring (anti addition).

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Demercuration Reaction

A hydride from sodium borohydride (NaBH4) replaces the mercuric acetate. In total, the oxymercuration-demercuration reaction gives the Markovnikov product. The hydroxy group on the most substituted carbon.
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OxymercurationDemercuration of 3,3,-Dimethyl-1-butene

The reaction does not suffer from rearrangements because there is no carbocation intermediate.
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AlkoxymercurationDemercuration
With alcohol (ROH) instead of water (HOH), the reaction produces an ether.

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Problem 3
Show the intermediates and products that result from alkoxymercurationdemercuration of 1-methylcyclopentene, using methanol as the solvent.
Solution

Chapter 8

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Hydroboration-oxidation of Alkenes

The reaction adds water across the double bond with anti-Markovnikov orientation. BH3 (borane) is a strong Lewis acid. BH3THF is the most commonly used form of borane. H2O2 is used for oxidation replacing boron with OH 21 group.

Mechanism of Hydroboration

Boron adds to the less substituted carbon and hydrogen adds to the more substituted carbon. The partial positive charge is on the more substituted carbon atom in the transition state .
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Oxidation to Alcohol

Oxidation of the alkyl borane with basic hydrogen peroxide produces the alcohol. In total, the hydroboration-oxidation gives the antiMarkovnikov alcohol product .
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Oxidation of a Trialkylborane

Chapter 8

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Stereochemistry of Hydroboration-Oxidation
CH3 BH3 THF CH3 H BH2 H2O2 NaOH CH3 H OH

The hydroboration steps adds the hydrogen and the boron to the same side of the double bond (syn addition). When the boron is oxidized, the OH will keep the same stereochemical orientation.

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Problem 4
Show how you would convert 1-methylcyclopentanol to trans-2-methylcyclopentanol.
Solution

1) BH3THF 2) H2O2, OH-

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hydroborationoxidation of a deuterium labeled norbornene

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Addition of Halogens

Cl2, Br2, and sometimes I2 add to a double bond to form a vicinal dihalide. This is an anti addition of halides.
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Mechanism of Halogen Addition to Alkenes

The intermediate is a three-membered ring called the halonium ion.

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Stereospecificity

meso

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Test for Unsaturation

Add Br2 in CCl4 (dark, redbrown color) to an alkene. The color quickly disappears as the bromine adds to the double bond. If there is no double bond, the brown color will remain.

An alkene

An alkane
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Formation of Halohydrin

A halohydrin is formed when halogen is added in the presence of water. Water is the nucleophile. Markovnikov addition: The partial positive bromine (electrophile) will add to the less substituted carbon. Bromonium ion intermediate Anti addition

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Mechanism of Halohydrin Formation

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Problem 5
Propose products and a mechanism for the reaction of 1-methylcyclopentene with bromine in water.
Solution

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Hydrogenation of Alkenes

Hydrogen (H2) can be added across the double bond in a process known as catalytic hydrogenation. The reaction only takes place if a catalyst is used. The most commonly used catalysts are palladium (Pd), platinum (Pt), and nickel (Ni). Syn addition of hydrogen.
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Mechanism of Catalytic Hydrogenation

The hydrogen and alkene are adsorbed on the metal surface. The hydrogens insert across the same face of the double bond The reduced product is released from the metal. 36 The result is syn addition of hydrogens.

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Chiral Hydrogenation Catalysts

Chiral catalysts are used to accomplish asymmetric induction, the selective creation of one enantiomer.
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Addition of Carbenes

The insertion of the CH2 group into a double bond produces a cyclopropane ring. 3 methods:
Diazomethane (CH3N2, UV light or heat). SimmonsSmith (CH2I2 and Zn(Cu)). Alpha elimination of a haloform (CHX3, NaOH, H2O).
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Diazomethane Method
N N CH 2 N N CH 2

diazomethane

heat or UV light

H N2 + C H carbene

CH 2

Problems with diazomentane: 1. Extremely toxic and explosive. 2. The carbene can insert into CH bonds too.
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SimmonsSmith Reaction
Best method for preparing cyclopropanes. CH2I2 + Zn(Cu) ICH2ZnI
SimmonsSmith reagent

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Alpha Elimination Reaction

In the presence of a base, chloroform or bromoform can be dehydrohalogenated to form a carbene.

H C CH3 C H CH3 CHBr3 KOH/H2O H CH3 Br Br CH3 H
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Retention of the cis or trans stereochemistry

Epoxidation

Alkene reacts with a peroxyacid to form an epoxide (also called oxirane). The usual reagent is peroxybenzoic acid.
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Mechanism

The peroxyacid and the alkene react with each other in a onestep reaction to produce the epoxide and a molecule of acid. The most common peroxyacid used is metachloroperoxybenzoic acid (MCPBA). 43

Retention Stereochemistry of Epoxidation

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Opening the Epoxide Ring

H

This process is acid catalyzed. Water attacks the protonated epoxide on the opposite side of the ring (back-side attack). Antidiol is formed.

O C C H 2O

OH C C O H H

OH C C O H H H2O

OH C C OH

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Syn Hydroxylation of Alkenes with OsO4

The OsO4 adds to the double bond of an alkene in a concerted mechanism forming an osmate ester. The osmate ester can be hydrolized to produce a syn-diol and regenerate the osmium tetroxide. 46

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Ozonolysis-Reduction

byproduct

Ozone will oxidatively cleave (break) the double bond to produce aldehydes and ketones. Ozonolysis will not oxidize aldehydes further (milder than KMnO4). A second step of the ozonolysis is the reduction of the intermediate by zinc or dimethyl sulfide. When dimethyl sulfide is used, DMSO is the byproduct. 47

Mechanism for the Formation of Ozonide

The ozone adds to the double bond, forming a fivemembered ring intermediate called molozonide, which rearranges to form the ozonide. Ozonide is very reactive and it is not isolated in the 48 ozonolysis reaction.

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Problem 6
Ozonolysisreduction of an unknown alkene gives an equimolar mixture of cyclohexanecarbaldehyde and 2-butanone. Draw the structure of the original alkene.

Solution

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Cleavage with KMnO4

Permanganate is a strong oxidizing agent. Glycol initially formed is further oxidized. Disubstituted carbons become ketones. Monosubstituted carbons become carboxylic acids. Terminal CH2 becomes CO2.
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Comparison of Permanganate Cleavage and Ozonolysis

carboxylate

Aldehydes can be isolated.

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Polymerization
An alkene (monomer) can add to another molecule like itself to form a polymer chain. Three methods:
Cationic, a carbocation intermediate Free radical Anionic, a carbanion intermediate

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Cationic Polymerization

Deprotonation (chain termination)

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Cationic Polymerization Using BF3 as Catalyst

The cation 54 is still living!

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Radical Polymerization

Free-radical polymerization occurs in the presence of an initiator such as peroxide.

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Anionic Polymerization

This require an alkene with strong electron-withdrawing groups such as nitro, cyano, or carbonyl attached to the double bond.
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