Alcohol Set Hers

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


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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


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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


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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


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Reduction of CarboxylicReduction of Carboxylic

Acids and EstersAcids and EstersLithium Aluminum HydrideLithium Aluminum Hydride

ReductionReduction

+-i l

'i l

+ '


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Hydration ofHydration of

AlkenesAlkenes

Acid catalyzed Hydration

xymercuration-Demercuration

Hydroboration- xidation


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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

+

'

''

+'

''


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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


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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


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Grignard AdditionGrignard AdditionReactionsReactions

Addition to Aldehydes/KetonesAddition to Aldehydes/Ketones

Addition to EstersAddition to Esters

Addition to EpoxidesAddition to Epoxides


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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


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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


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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


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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


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Conversion ofConversion of

Alcohols to SaltsAlcohols to Salts

Reaction with Active MetalsReaction with Active Metals

O O N + + 2


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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


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Oxidation of AlcoholsOxidation of Alcohols

rimary

Mnorr

7

econdaryor

Mnor

r 7

Tertiaryor

Mn

no reaction


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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


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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


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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


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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


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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


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HaloformR

eactionHaloformR

eactionMethyl carbinol cleavage to giveMethyl carbinol cleavage to giveCarboxylic acids and HaloformCarboxylic acids and Haloform

2

-

2

-


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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)


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SpectroscopicSpectroscopicCharacteristics of AlcoholsCharacteristics of Alcohols

InfraredInfrared

PmrPmr

CmrCmr


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EthersEthers NomenclatureNomenclature

PropertiesProperties

PreparationPreparation

ReactionsReactions

NomenclatureNomenclature

PropertiesProperties

PreparationPreparation

ReactionsReactions


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EtherEther

NomenclatureNomenclature


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Preparation of EthersPreparation of EthersDehydration of AlcoholsDehydration of Alcohols

Williamson synthesisWilliamson synthesisAlkoxymercurationAlkoxymercuration--

DemercurationDemercuration

Peroxyacid Epoxidation ofPeroxyacid Epoxidation of

AlkenesAlkenes


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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+

-


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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


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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


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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


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Ether ReactionsEther Reactions

H CleavageH Cleavage

Epoxide Ring OpeningEpoxide Ring Opening


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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


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Epoxide Ring OpeningEpoxide Ring Opening

Unimolecular or BimolecularUnimolecular or Bimolecular

1

2

-

- 22

2

Alcohol Set Hers

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