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ORGANIC CHEMISTRY

Dr Nam T. S. Phan

Faculty of Chemical Engineering

HCMC University of Technology

Office: room 211, B2 Building

Phone: 38647256 ext. 5681

Email: ptsnam@hcmut.edu.vn

Chapter 5: ALKENES

An sp 2 hybridized carbon
An sp 2
hybridized
carbon

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NOMENCLATURE OF ALKENES

The IUPAC name of an alkene is obtained by replacing the “ane” ending of the corresponding alkane with “ene”

NOMENCLATURE OF ALKENES The IUPAC name of an alkene is obtained by replacing the “ane” ending

Ethylene is an acceptable synonym for ethene in the IUPAC system

Propylene, isobutylene and other common names ending in ylene” are NOT acceptable IUPAC names

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Determine the parent hydrocarbon – the longest continuous carbon chain containing the C=C 4

Determine the parent hydrocarbon – the

longest continuous carbon chain containing the C=C

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Note: Alkenes can have geometric isomers

Note: Alkenes can have geometric isomers 5

PREPARATION OF ALKENES

Dehydrations of alcohols

Acid

PREPARATION OF ALKENES Dehydrations of alcohols Acid isomerization 6
PREPARATION OF ALKENES Dehydrations of alcohols Acid isomerization 6

isomerization

6

isomerization 7

isomerization

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Eliminations of alkyl halides

Eliminations of alkyl halides Base 8

Base

Alkyne hydrogenations

Pd/CaCO 3 + Pb(OAc) 2 / quinoline

Alkyne hydrogenations Pd/CaCO + Pb(OAc) / quinoline 9

REACTIONS OF ALKENES

Additions of hydrogen halides (A E )

REACTIONS OF ALKENES Additions of hydrogen halides (A ) More stable Markovnikov’s rule 10

More stable

Markovnikov’s rule

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Carbocation rearrangement

More stable

Carbocation rearrangement More stable 11
Carbocation rearrangement More stable 11

More stable

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Stereochemistry
Stereochemistry

Racemic mixture

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Already has 1 asymmetric carbon 14

Already has 1 asymmetric carbon

2 asymmetric carbons are created

2 asymmetric carbons are created 15

Additions of hydrogen bromide (A R ) Electrophilic addition (A E)

Additions of hydrogen bromide (A ) Electrophilic addition (A Radical addition (A ) – only for
Additions of hydrogen bromide (A ) Electrophilic addition (A Radical addition (A ) – only for

Radical addition (A R ) – only for HBr

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Reaction

mechanism:

Additions of halogens

Major addition product – NOT a dihalide 19

Major addition product –

NOT a

dihalide

Stereochemistry

Stereochemistry

Stereochemistry 2 asymmetric carbons are created Trans -2-butene meso compound 22

2 asymmetric carbons are created

Stereochemistry 2 asymmetric carbons are created Trans -2-butene meso compound 22

Trans-2-butene meso compound

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Additions of water – hydration reactions

Water is too weakly acidic to allow the hydrogen to act as an electrophile

Additions of water – hydration reactions Water is too weakly acidic to allow the hydrogen to
Additions of water – hydration reactions Water is too weakly acidic to allow the hydrogen to

Markovnikov’s rule

Additions of water – hydration reactions Water is too weakly acidic to allow the hydrogen to

H 2 SO 4 , H 3 PO 4

Reaction

mechanism:

Carbocation rearrangement might occur

Reaction mechanism: Carbocation rearrangement might occur 24

Alcohols by oxymercuration-reduction

Alcohols by oxymercuration-reduction Markovnikov’s rule No carbocation formation, no rearrangement 25

Markovnikov’s rule

Alcohols by oxymercuration-reduction Markovnikov’s rule No carbocation formation, no rearrangement 25

No carbocation formation, no rearrangement

Alcohols by oxymercuration-reduction Markovnikov’s rule No carbocation formation, no rearrangement 25

Additions of borane: hydroboration-oxidation

Additions of borane: hydroboration-oxidation 26

Regioselectivity:

Regioselectivity: Anti-Markovnikov 27
Regioselectivity: Anti-Markovnikov 27

Anti-Markovnikov

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Additions of hydrogen – hydrogenation

Additions of hydrogen – hydrogenation 28

Reaction mechanism:

Syn addition

Stereochemistry

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Alkene epoxidations – Anti hydroxylations

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32

Stereochemistry

Stereochemistry 33

Reactions of epoxides

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35

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Stereochemistry

Anti additions

Stereochemistry Anti additions 36

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Syn hydroxylations of alkenes

Syn hydroxylations of alkenes 37

Reaction mechanism:

Syn additions

Reaction mechanism: 38

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Permanganate cleavage of alkenes

Permanganate cleavage of alkenes 39

Ozonolysis of alkenes

Ozonolysis of alkenes 40
In the presence of an oxidizing agent , the products will be ketones / carboxylic acids

In the presence of an oxidizing agent, the products will be ketones / carboxylic acids

Polymerizations