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Chapter 7.

Alkenes: Reactions

and Synthesis

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)

Reactions of Alkenes
H X OH Alcohol Alkane Halohydrin HO OH OH H H

X C C

1,2-Diol

1,2-Dihalide

alkene O

Carbonyl Compound

Halide O

Epoxide

Cyclopropane

Preparation of Alkenes
Addition
X C C Y C C

+X

Elimination
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Part 1 - Synthesis of Alkenes


These reactions are used to produce alkenes.

Synthesis of Alkenes: Synthesis 1#


Alkenes are commonly made by elimination of HX from alkyl halide (dehydrohalogenation) Uses heat and KOH

H H H Br KOH CH 3CH 2OH

H H

+ KBr +

H2O

Synthesis of Alkenes: Synthesis 2#


elimination of H-OH from an alcohol (dehydration) require strong acids (sulfuric acid, 50 C)

CH 3 OH

H2SO4, H2O THF, 50 oC

CH 3

H2O

Part 2 - Reaction of Alkenes


These reactions react alkenes to form a series of alkane products.

Addition of Halogens to Alkenes


Bromine and chlorine add to alkenes to give 1,2dihaldes F2 is too reactive and I2 does not add.

Cl H H C C H H

Cl Cl Cl H C C H H H

Example: Mechanism of Bromine Addition


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. Gives trans addition.
Br Br + C C

Br C C

+ Br -

Br C C Br -

Br C C Br

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Example: Addition of Br2 to Cyclopentene


found

H
Addition is exclusively trans

Br H Br H
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Br H H Br Br Br H

not found

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)

C C
Alkene

X2 H2O

X C C HO
Halohydrin
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+ HX

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.
O N Br (NBS) O H2O, CH 3SOCH 3(DMSO) OH Br

2-Bromo-1-phenylethanol (76%)

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Addition of Water to Alkenes: Oxymercuration


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

H O H + C C

H3PO 4 HO 250oC

H H

H H H

H HO H

H H H

Intermediate
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Addition of Water to Alkenes: Oxymercuration

H CH 3 Hg(OAc) 2 HgOAc CH 3 H2O

H HgOAc CH 3 OH

NaBH 4

H H CH 3 OH

Hg(OAc)2 is used as an electrophillic sink. The double bond is then attacked by the water creating an alchohol. This is then REDUCED by NaBH4 that adds an H to the molecule.

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Addition of Water to Alkenes: Hydroboration


Herbert Brown (HB) invented hydroboration (HB) Borane (BH3) is electron deficient is a Lewis acid. Borane adds to an alkene to give an organoborane.

H B

+ H

C C

BH2

Borane

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 Alcohol Formation from Alkenes


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)

H H B H CH 3 1-methylcycopentene BH 3 THF H CH 3 Alkylborane intermediate

OH

H OH H CH 3 trans-2-methylcyclopentanol (85%)

H2O2

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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, 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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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
R1 C R2 Carbene R1 C R2

Alkene

Cyclopropane
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Formation of Dichlorocarbene
Base removes proton from chloroform Stabilized carbanion remains Unimolecular Elimination of Clgives electron deficient species, dichlorocarbene

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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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Reaction of Dichlorocarbene
Addition of dichlorocarbene is stereospecific cis

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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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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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Oxidation of Alkenes: Hydroxylation and Cleavage


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)

C C Alkene

1. OsO4 2. NaHSO3

HO

OH

A 1,2-diol
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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
Intermediate CH 3 CH 3 CH 3 O O Os O O CH 3 A cyclic osmate CH 3 OH OH CH 3 A 1,2-diol (87%) NAME THIS MOLECULE

1. OsO4 pyridine

2. NaHSO3 H2O

NAME THIS MOLECULE

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Section 3: Breakdown of Alkenes


These Reactions are used to breakdown alkenes into two products.

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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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Structure Elucidation With Ozone


Cleavage products reveal an alkenes structure

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Permanganate 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
O O + H H O

+ KMnO 4

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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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Biological Alkene Addition Reactions


Living organisms convert organic molecules using enzymes as catalysts Many reactions are similar to organic chemistry conversions, except they occur in neutral water Usually much specific for reactant and stereochemistry

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Biological Hydration Example


Fumarate to malate catalyzed by fumarase Specific for trans isomer Addition of H, OH is anti
O O O O H OH Fumarase O O H OH O O

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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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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 non-radical 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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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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Take Home Message


Learn the REACTIONS (ALL OF THEM)

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Synthesis of Alkenes
1) dehydrohalogenation
H H H Br KOH CH 3CH 2OH H H

+ KBr +

H2O

2) dehydration

CH 3 OH

H2SO4, H2O THF, 50 C


o

CH 3

H2O

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Part 2 - Reaction of Alkenes


1) Addition of Halogens to Alkenes

C C

X2 H2O

X C C HO + HX

2) Halohydrin Formation

H H C C H H

+ Cl
O

Cl

Cl Cl H C C H H H

N Br (NBS) O H2O, CH 3SOCH 3(DMSO)

OH Br

2-Bromo-1-phenylethanol (76%)

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Part 2 - Reaction of Alkenes


3) Addition of Water to Alkenes
H H B H CH 3 1-methylcycopentene BH 3 THF H CH 3 Alkylborane intermediate
-

OH

H OH H CH 3 trans-2-methylcyclopentanol (85%)

H2O2

4) Hydroboration-Oxidation Alcohol Formation


C C H + O H H3PO 4 250oC H HO H H H H

5) Carbene Formation Cyclopropane synthesis


R1 C R2 Carbene R1 C R2

Alkene

Cyclopropane

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Part 2 - Reaction of Alkenes


6) Catalytic Hydrogenation

7) Hydroxylation and Cleavage

C C Alkene

1. OsO4 2. NaHSO3

HO

OH

A 1,2-diol

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Part 3 - Breakdown of Alkenes


1) Ozonolysis

2) Permangante Oxidation
+ KMnO 4 O O + H H O O

3) Periodic Acid Oxidation, Cleavage of 1,2-diols

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