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Lecture
Reactions of Alcohols
Chapter 11
Dehydration to alkene
Oxidation to aldehyde, ketone
Substitution to form alkyl halide
Reduction to alkane
Esterification
Tosylation
Williamson synthesis of ether
Chapter 11
Summary Table
Chapter 11
Oxidation States
Inorganic chemistry:
Oxidation is a loss of electrons.
Reduction is a gain of electrons.
Organic chemistry
Oxidation: Gain of O, O2, or X2; loss of H2.
Reduction: Gain of H2 (or H); loss of O or O2; and loss
of X2.
Neither: The gain or loss of H+, H2O, OH, HX, etc. is
neither an oxidation nor a reduction.
Chapter 11
Chapter 11
Oxidation of 2 Alcohols
A 2 alcohol becomes a
ketone.
Traditional oxidizing agents
are chromium- based
reagents such as Na2Cr2O7
in H2SO4.
Active reagent probably is
H2CrO4 or HCrO4.
Color change is orange to
greenish-blue.
Chromium is highly toxic
and difficult to dispose of
properly.
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Chapter 11
Oxidation Mechanism
Chapter 11
Oxidation of 1 Alcohols to
Carboxylic Acids
Chapter 11
Pyridinium Chlorochromate
(PCC)
pyridinium ion
chlorochromate ion
CrO3 + HCl +
Pyridine
ClCrO3 -
N
H
Pyridinium chlorochromate
(PCC)
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Pyridinium Chlorochromate
(PCC)
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OH
PCC
Geraniol
OH
Menthol
O
H
Geranial
PCC
Menthone
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Swern Oxidation
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Dess-Martin Periodinane
(DMP)
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Solved Problem 1
Suggestthemostappropriatemethodforeachofthefollowinglaboratorysyntheses:
(a)cyclopentanol>cyclopentanone
Solution
Manyreagentsareavailabletooxidizeasimplesecondaryalcoholtoaketone.Foralaboratory
synthesis,however,dehydrogenationisnotpractical,andcostisnotaslargeafactorasitwouldbein
industry.Mostlabswouldhavechromiumtrioxideorsodiumdichromateavailable,andthechromic
acidoxidationwouldbesimple.PCCandtheSwernoxidationwouldalsowork,althoughthese
reagentsaremorecomplicatedtoprepareanduse.
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Solution
Thissynthesisrequiresmorefinesse.Thealdehydeiseasilyoveroxidizedtoacarboxylicacid,andthe
doublebondreactswithoxidantssuchasKMnO4.OurchoicesarelimitedtoPCCortheSwern
oxidation.
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Alcohol as a Nucleophile
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Alcohol as an Electrophile
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Tosylate Esters
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Summary of Tosylate
Reactions
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Reduction of Alcohols
Dehydrate with concentrated H2SO4, then add H2.
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OH of alcohol is protonated.
OH2+ is good leaving group.
3 and 2 alcohols react with Br via SN1.
1 alcohols react via SN2.
2013 Pearson Education, Inc.
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SN1 Mechanism
Step 1: Protonation.
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SN2 Mechanism
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Limitations of HX Reactions
Poor yields of alkyl chlorides from
primary and secondary alcohols.
Elimination competes with substitution.
Carbocation intermediate may undergo
a rearrangement.
Limited ability to make alkyl halides.
Chapter 11
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Solved Problem 2
When3methyl2butanolistreatedwithconcentratedHBr,themajorproductis2bromo2
methylbutane.Proposeamechanismfortheformationofthisproduct.
Solution
Thealcoholisprotonatedbythestrongacid.Thisprotonatedsecondaryalcoholloseswatertoforma
secondarycarbocation.
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Reactions with
Phosphorus Halides
Good yields with 1 and 2 alcohols.
PCl3 for alkyl chlorides (but SOCl2 better).
PBr3 for alkyl bromides.
P and I2 for alkyl iodides (PI3 not stable).
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Examples
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Dehydration Reactions
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Dehydration of Alcohols
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Mechanism of Dehydration: E1
Step 1: Protonation.
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Energy Diagram, E1
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Solved Problem 3
Predicttheproductsofsulfuricacidcatalyzeddehydrationof1methylcyclohexanol
Solution
1Methylcyclohexanolreactstoformatertiarycarbocation.Aprotonmaybeabstractedfromany
oneofthreecarbonatoms.Thetwosecondaryatomsareequivalent,andabstractionofaproton
fromoneofthesecarbonsleadstothetrisubstituteddoublebondofthemajorproduct.
Abstractionofamethylprotonleadstothedisubstituteddoublebondoftheminorproduct.
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Pinacol Rearrangement
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Esterification
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Fischer Esterification
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Nitrate Esters
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Phosphate Esters
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