8/8/2019 Alcohol Set Hers
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AlcoholsAlcohols
Nomenclature Properties
Preparation
Reactions
Spectroscopy
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Alcohol
NomenclatureIUPACIUPAC
CommonCommon
CarbinolCarbinol
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PreparationPreparationReactionsReactions
Reduction of carbonyl compoundsReduction of carbonyl compounds
Hydration of AlkenesHydration of Alkenes
Grignard reactionsGrignard reactions
8/8/2019 Alcohol Set Hers
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Reduction of CarbonylReduction of CarbonylCompoundsCompounds
Reduction of Aldehydes/ketonesReduction of Aldehydes/ketones
Reduction of Carboxylic acids/EstersReduction of Carboxylic acids/Esters
8/8/2019 Alcohol Set Hers
5/38
Reduction ofReduction of
Aldehydes/KetonesAldehydes/Ketones
HydrogenationHydrogenation
R
O
H R H 2OHH 2
tri ary ROH
R
O
R'H 2
tR
OH
HR' econdary ROH
8/8/2019 Alcohol Set Hers
6/38
Reduction of Aldehydes/KetonesReduction of Aldehydes/Ketones
Hydride ReductionsHydride Reductions
R HLi H4
R R'Li H4 R
H
HR' econd ry R H
orBH4
or
BH4
R H H ri ry R H
8/8/2019 Alcohol Set Hers
7/38
Reduction of CarboxylicReduction of Carboxylic
Acids and EstersAcids and EstersLithium Aluminum HydrideLithium Aluminum Hydride
ReductionReduction
+-i l
'i l
+ '
8/8/2019 Alcohol Set Hers
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Hydration ofHydration of
AlkenesAlkenes
Acid catalyzed Hydration
xymercuration-Demercuration
Hydroboration- xidation
8/8/2019 Alcohol Set Hers
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AcidAcid--Catalyzed HydrationCatalyzed Hydration
of Alkenesof Alkenes Markovnikov additionMarkovnikov addition
Formation of most stable carbocationFormation of most stable carbocation
Shifts/rearrangements possibleShifts/rearrangements possible
+
'
''
+'
''
8/8/2019 Alcohol Set Hers
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Hydration of Alkenes viaHydration of Alkenes via
Oxymercuration/DemercurationOxymercuration/Demercuration Markovnikov additionMarkovnikov addition
Typically no shifts/rearrangementsTypically no shifts/rearrangements
Mercurinium ion involvementMercurinium ion involvement
2OO
'
''
O
'
''
g(O c) 2 a
2O
g(O c) 2 a
8/8/2019 Alcohol Set Hers
11/38
HydroborationHydroboration--OxidationOxidation
of Alkenesof Alkenes AntiAnti--Markovnikov additionMarkovnikov addition
No shifts/rearrangementsNo shifts/rearrangements
Syn additionSyn addition
'
''
'
''
( 3)2-
2 2
( 3)2-
2 2
8/8/2019 Alcohol Set Hers
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Grignard AdditionGrignard AdditionReactionsReactions
Addition to Aldehydes/KetonesAddition to Aldehydes/Ketones
Addition to EstersAddition to Esters
Addition to EpoxidesAddition to Epoxides
8/8/2019 Alcohol Set Hers
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Grignard Additions toAldehydes/KetonesGrignard Additions toAldehydes/Ketones
Formation of primary, secondary, andFormation of primary, secondary, and
tertiary alcoholstertiary alcohols
MgX rimary
MgX
MgX
''
' " '
"
econdary
Tertiary
8/8/2019 Alcohol Set Hers
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Grignard Additions to EstersGrignard Additions to EstersFormation of secondary and
tertiary alcohols
H C
O
OR R'2 R'2CHOH + ROH
Secondary ROH
R'+ 2R" C
O
OR R" CR'
R'
OH + ROH
Teriary ROH
8/8/2019 Alcohol Set Hers
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Grignard Addition toGrignard Addition to
EpoxidesEpoxides
O+ RMgX RCH 2 CH 2 OH
O
R' R'
+ RMgX R' C
R
H
C R'
OH
H
Primary ROH
Secondary ROH
OR'
R'
R'
R'
+ RMgX R' C
R
C R'
OH
R' R'
ertiary ROH
8/8/2019 Alcohol Set Hers
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Typical Alcohol ReactionsTypical Alcohol Reactions
Salt formationSalt formation
DehydrationDehydrationOxidationOxidation
Alkyl halideAlkyl halide
formationformationEster formationEster formation
Ether synthesisEther synthesis
Periodic acidPeriodic acidcleavage of glycolscleavage of glycols
Haloform reaction ofHaloform reaction of
methyl carbinolsmethyl carbinolsTHP acetal formationTHP acetal formation
8/8/2019 Alcohol Set Hers
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Conversion ofConversion of
Alcohols to SaltsAlcohols to Salts
Reaction with Active MetalsReaction with Active Metals
O O N + + 2
8/8/2019 Alcohol Set Hers
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Dehydration of AlcoholsDehydration of Alcohols
E-1 E-2
R C C
H
H
OHH
+
R C C
H
H
OH 2+
R C C
H
H
OH 2+
H 2O
rdsR C C
H
H
+
R C C
H
H
+ H + R C
H
C
1,2-shifts/rearrangements p ssible
R C C
H
H
OHPOCl 3
R C C
H
H
OPOCl 2
N
R C C
H
H
OPOCl 2 R C
H
C
adi hl rophosphate
intermediate
Anti periplanar( oplanar)elimination
No1,2-shifts/rearrangements possible
8/8/2019 Alcohol Set Hers
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Oxidation of AlcoholsOxidation of Alcohols
rimary
Mnorr
7
econdaryor
Mnor
r 7
Tertiaryor
Mn
no reaction
8/8/2019 Alcohol Set Hers
20/38
Alcohol Conversion toAlcohol Conversion to
Alkyl HalidesAlkyl Halides
Reaction with Hydrogen halidesReaction with Hydrogen halides
Reaction with Thionyl chlorideReaction with Thionyl chloride
Reaction with PhosphorusReaction with Phosphorus
trihalides or pentahalidestrihalides or pentahalides
8/8/2019 Alcohol Set Hers
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Hydrogen Halide Conversion ofHydrogen Halide Conversion of
Alcohols to Alkyl HalidesAlcohols to Alkyl Halides
1
re i a tl
re i a tl
1 r
w ere = I, r, r l
8/8/2019 Alcohol Set Hers
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Conversion of Alcohols to AlkylConversion of Alcohols to Alkyl
Chlorides via Thionyl ChlorideChlorides via Thionyl Chloride
primar rsec ar
alc h l
l2l
alk l chl r sulfite
l-
2l
2 l
8/8/2019 Alcohol Set Hers
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Conversion of Alcohols to AlkylConversion of Alcohols to Alkyl
Halides via Phosphorus HalidesHalides via Phosphorus Halides
rimary or
secondary
alco ol
C OH C O
H
PX 2S 2
C X HOPX 2+
+
X-
PX 3
rotonated
al yl di alo os ite
8/8/2019 Alcohol Set Hers
24/38
8/8/2019 Alcohol Set Hers
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Periodic Acid Cleavage ofPeriodic Acid Cleavage of
GlycolsGlycols
H C
H
H
C
H
H
HHIO
4
+ HIO3
HIO4
+ HIO3C
OH
H
C
OH
H
R R
HIO4
+ HIO3C
OH
C
OH
R R
R R
H C H
O
2
2 C H
O
R
2 C
O
R R
8/8/2019 Alcohol Set Hers
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HaloformR
eactionHaloformR
eactionMethyl carbinol cleavage to giveMethyl carbinol cleavage to giveCarboxylic acids and HaloformCarboxylic acids and Haloform
2
-
2
-
8/8/2019 Alcohol Set Hers
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Disguising an AlcoholDisguising an Alcohol
Creating a tetrahydropyranyl acetalCreating a tetrahydropyranyl acetal
O
+ ROHH
+
ORO
Overall Transformation
(an acetal)
Mechanism
-
(a heteroatom-stabilized carbocation)
-
Dihydropyran(DHP)
8/8/2019 Alcohol Set Hers
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SpectroscopicSpectroscopicCharacteristics of AlcoholsCharacteristics of Alcohols
InfraredInfrared
PmrPmr
CmrCmr
8/8/2019 Alcohol Set Hers
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EthersEthers NomenclatureNomenclature
PropertiesProperties
PreparationPreparation
ReactionsReactions
NomenclatureNomenclature
PropertiesProperties
PreparationPreparation
ReactionsReactions
8/8/2019 Alcohol Set Hers
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EtherEther
NomenclatureNomenclature
8/8/2019 Alcohol Set Hers
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Preparation of EthersPreparation of EthersDehydration of AlcoholsDehydration of Alcohols
Williamson synthesisWilliamson synthesisAlkoxymercurationAlkoxymercuration--
DemercurationDemercuration
Peroxyacid Epoxidation ofPeroxyacid Epoxidation of
AlkenesAlkenes
8/8/2019 Alcohol Set Hers
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Ether Formation via AcidEther Formation via Acid
Catalyzed Dehydration ofCatalyzed Dehydration of
AlcoholsAlcohols
2H
+
2
C +H+
C H2
C R
H
+
R H
+C H
2
H2
-
C RC R
H
+
+
H2
H+
-
H+
-
8/8/2019 Alcohol Set Hers
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Williamson Synthesis of EthersWilliamson Synthesis of Ethers
Bimolecular Substitution by Alkoxide
on a suitable substrate
RO-
Na+
+ R C
H
H
RO C
H
H
R +Na
Primary
Alkyl Halide
SN
2
8/8/2019 Alcohol Set Hers
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AlkoxymercurationAlkoxymercuration--
Demercuration of AlkenesDemercuration of Alkenes Markovnikov AdditionMarkovnikov Addition Typically no rearrangements/shiftsTypically no rearrangements/shifts
Mercurinium ion involvementMercurinium ion involvement
R C C H
H H
R C C
H
H
H
H
OR'
R C C
HR'
R'' R C C
H
R'
R''
H
OR'
a H 4
a H 4
R'OH
R'OH
MMR
MMR
Where MMR modified mercury reagent Mercury trifluoroacetate
8/8/2019 Alcohol Set Hers
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Epoxidation of AlkenesEpoxidation of Alkenes
C
H
C
H
R R
H
RR
H
O
CC
R C
O
O H
O
HO
C
R O
Prilezhaev reactionPrilezhaev reaction
8/8/2019 Alcohol Set Hers
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Ether ReactionsEther Reactions
H CleavageH Cleavage
Epoxide Ring OpeningEpoxide Ring Opening
8/8/2019 Alcohol Set Hers
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HXCleavage of EthersHXCleavage of EthersHXCleavage of EthersHXCleavage of Ethers
Unimolecular or BimolecularUnimolecular or Bimolecular
Cleavage PathwaysCleavage Pathways
R O R H R O R
H
+
X-
SN
SN
2
R O R
H
+
R O R
H
+
X-
ROHR
+ X-
RX
RX ROH+
Protonation
8/8/2019 Alcohol Set Hers
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Epoxide Ring OpeningEpoxide Ring Opening
Unimolecular or BimolecularUnimolecular or Bimolecular
1
2
-
- 22
2
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