AlcoholsAlcohols Nomenclature Properties Preparation Reactions Spectroscopy

Alcohol Nomenclature

IUPACIUPAC

CommonCommon

CarbinolCarbinol

Preparation Preparation ReactionsReactions

Reduction of carbonyl compoundsReduction of carbonyl compounds Hydration of AlkenesHydration of Alkenes Grignard reactionsGrignard reactions

Reduction of Carbonyl Reduction of Carbonyl CompoundsCompounds

Reduction of Aldehydes/ketonesReduction of Aldehydes/ketones Reduction of Carboxylic acids/EstersReduction of Carboxylic acids/Esters

Reduction of Reduction of Aldehydes/KetonesAldehydes/Ketones

HydrogenationHydrogenation

R CO

H RCH2OHH2

Pt Primary ROH

R CO

R'H2Pt

R COH

HR' Secondary ROH

Reduction of Aldehydes/KetonesReduction of Aldehydes/Ketones

Hydride ReductionsHydride Reductions

R CO

HLiAlH4

R CO

R'LiAlH4 R C

OH

HR' Secondary ROH

orNaBH4

or NaBH4

RCH2OH Primary ROH

Reduction of Carboxylic Reduction of Carboxylic Acids and EstersAcids and Esters

Lithium Aluminum Hydride Lithium Aluminum Hydride ReductionReduction

R C

O

OH RCH2OH +OH-LiAlH4

R C

O

OR'LiAlH4

RCH2OH + R'OH

Hydration of Hydration of AlkenesAlkenes

Acid catalyzed Hydration Oxymercuration-Demercuration Hydroboration-Oxidation

Acid-Catalyzed Hydration Acid-Catalyzed Hydration of Alkenesof Alkenes

Markovnikov additionMarkovnikov addition Formation of most stable carbocationFormation of most stable carbocation Shifts/rearrangements possibleShifts/rearrangements possible

R C C H

H HH+

H2OR C C

H

H

H

H

OH

R C C

HR'

R''H+

H2OR C C

H

HOH

R'

R''

Hydration of Alkenes via Hydration of Alkenes via Oxymercuration/DemercurationOxymercuration/Demercuration

Markovnikov additionMarkovnikov addition Typically no shifts/rearrangementsTypically no shifts/rearrangements Mercurinium ion involvementMercurinium ion involvement

R C C H

H H

H2OR C C

H

H

H

H

OH

R C C

HR'

R'' R C C

H

HOH

R'

R''

Hg(OAc)2 NaBH4

H2O

Hg(OAc)2 NaBH4

Hydroboration-Oxidation Hydroboration-Oxidation of Alkenesof Alkenes

Anti-Markovnikov additionAnti-Markovnikov addition No shifts/rearrangementsNo shifts/rearrangements Syn additionSyn addition

R C C H

H H

R C C

H

H

H

H OH

R C C

HR'

R'' R C C

HR'

R''

H OH

(BH3)2 OH-

H2O2

(BH3)2 OH-

H2O2

Grignard Grignard Addition Addition

ReactionsReactions Addition to Aldehydes/KetonesAddition to Aldehydes/Ketones Addition to EstersAddition to Esters Addition to EpoxidesAddition to Epoxides

Grignard Additions to Grignard Additions to Aldehydes/KetonesAldehydes/Ketones

Formation of primary, secondary, and Formation of primary, secondary, and tertiary alcoholstertiary alcohols

H C H

O

RMgXRCH2OH Primary ROH

RMgX

RMgX

R' C

OH

H

RR'

O

HC

R' R"

O

C R' C

OH

R

R"

Secondary ROH

Tertiary ROH

Grignard Additions to EstersGrignard Additions to EstersFormation of secondary and

tertiary alcohols

H C

O

OR R'MgX+ 2 R'2CHOH +ROHSecondary ROH

R'MgX+ 2R" C

O

OR R" C

R'

R'

OH +ROH

Teriary ROH

Grignard Addition to Grignard Addition to EpoxidesEpoxides

O +RMgX RCH2CH2OH

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'Tertiary ROH

Typical Alcohol Typical Alcohol ReactionsReactions

Salt formationSalt formation DehydrationDehydration OxidationOxidation Alkyl halide Alkyl halide

formationformation Ester formationEster formation

Ether synthesisEther synthesis Periodic acid cleavage Periodic acid cleavage

of glycolsof glycols Haloform reaction of Haloform reaction of

methyl carbinolsmethyl carbinols THP acetal formation THP acetal formation

Conversion of Conversion of Alcohols to Alcohols to

SaltsSaltsReaction with Active MetalsReaction with Active Metals

ROHNa

RO- Na++H2

Dehydration of AlcoholsDehydration of Alcohols

E-1 E-2

R C C

H

H

OHH+

R C C

H

H

OH2+

R C C

H

H

OH2+

H2Ords R C C

H

H+

R C C

H

H+ H+

R C

H

C

1,2-shifts/rearrangements possible

R C C

H

H

OHPOCl3

R C C

H

H

OPOCl2

N

R C C

H

H

OPOCl2 R C

H

C

a dichlorophosphate intermediate

Anti periplanar (coplanar) eliminationNo 1,2-shifts/rearrangements possible

Oxidation of Oxidation of AlcoholsAlcohols

Primary RCH2OH

RCHO

RCOOH

PCC

KMnO4 or

K2Cr2O7∆

SecondaryR2CHOHPCC or

KMnO4or

K2Cr2O7∆

R C

O

R

Tertiary R3COHPCC or

KMnO4∆

no reaction

Alcohol Conversion to Alcohol Conversion to Alkyl HalidesAlkyl Halides

Reaction with Hydrogen halidesReaction with Hydrogen halidesReaction with Thionyl chlorideReaction with Thionyl chlorideReaction with Phosphorus Reaction with Phosphorus

trihalides or pentahalidestrihalides or pentahalides

Hydrogen Halide Conversion of Hydrogen Halide Conversion of Alcohols to Alkyl HalidesAlcohols to Alkyl Halides

RCH2OH HX RCH2X

SN1

SN2 predominantly

predominantly

SN1 SN2orHX

HX

R2CHOH R2CHX

R3COH R3CX

where HX = HI, HBr, or HCl

Conversion of Alcohols to Conversion of Alcohols to Alkyl Chlorides via Thionyl Alkyl Chlorides via Thionyl

Chloride Chloride

primary or secondaryalcohol

C OHSOCl2

C O S

O

Cl

alkyl chlorosulfite

Cl-

SN2C Cl +SO2 +HCl

Conversion of Alcohols to Conversion of Alcohols to Alkyl Halides via Alkyl Halides via

Phosphorus HalidesPhosphorus Halides

primary or secondaryalcohol

C OH C O

H

PX2 SN

2C X HOPX2+

+

X-PX3

protonatedalkyl dihalophosphite

Ester Formation from AlcoholsEster Formation from Alcohols

R C

O

ClR'OH

R C

O

OR'+

R C

O

OHR'OH

R C

O

OR'+H+

R C

O

O C

O

RR'OH

R C

O

OR'+R C OH

O

HCl

H2O

Periodic Acid Cleavage of Periodic Acid Cleavage of GlycolsGlycols

H C

OH

H

C

OH

H

H HIO4+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'

Haloform ReactionHaloform ReactionMethyl carbinol cleavage to give Methyl carbinol cleavage to give

Carboxylic acids and HaloformCarboxylic acids and Haloform

CH3 C

OH

H

HX2

OH-H+

H C

O

OHHCX3 +

CH3 C

OH

H

RX2

OH-H+

HCX3 + C

O

OHR

Disguising an AlcoholDisguising an AlcoholCreating a tetrahydropyranyl acetalCreating a tetrahydropyranyl acetal

O+ ROH

H+

ORO

Overall Transformation

(an acetal)

Mechanism

O

H+

H+- O

H

H+ O

H

H +

O+OHR +

OOR

H+

(a heteroatom-stabilized carbocation)

H+

H+-

OOR

Dihydropyran(DHP)

Spectroscopic Spectroscopic CharacteristicCharacteristics of Alcoholss of Alcohols

InfraredInfrared PmrPmr CmrCmr

EtherEtherss

EtherEtherss NomenclatureNomenclature

PropertiesProperties PreparationPreparation ReactionsReactions

NomenclatureNomenclature PropertiesProperties PreparationPreparation ReactionsReactions

Ether Ether NomenclatureNomenclature

Ether Ether NomenclatureNomenclature

Preparation of EthersPreparation of Ethers Dehydration of AlcoholsDehydration of Alcohols

Williamson synthesisWilliamson synthesis

Alkoxymercuration- Alkoxymercuration- DemercurationDemercuration

Peroxyacid Epoxidation of Peroxyacid Epoxidation of AlkenesAlkenes

Ether Formation via Acid Ether Formation via Acid Catalyzed Dehydration of Catalyzed Dehydration of

AlcoholsAlcohols

ROH2H+

R O R

S

S

N

N

1

2

C +ROH+

C OH2 C OR

H

+

ROH

+C OH2

H2O-

C O RC OR

H

+

+

H2O

H+-

H+-

Williamson Synthesis of EthersWilliamson Synthesis of Ethers

Bimolecular Substitution by Alkoxide on a suitable substrate

RO- Na++R' C

H

H

X RO C

H

H

R' +NaX

Primary

Alkyl Halide

SN2

Alkoxymercuration-Alkoxymercuration-Demercuration of Demercuration of

AlkenesAlkenes 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'

NaBH4

NaBH4

R'OH

R'OH

MMR

MMR

Where MMR = modified mercury reagentMercury trifluoroacetate=

Epoxidation of AlkenesEpoxidation of Alkenes

CH

CH

R R

HRR

H

O

CC

R C

O

O H

O

HO

CR O

Prilezhaev reactionPrilezhaev reaction

Ether ReactionsEther Reactions

HX CleavageHX Cleavage Epoxide Ring OpeningEpoxide Ring Opening

HX Cleavage of HX Cleavage of EthersEthers

HX Cleavage of HX Cleavage of EthersEthers

Unimolecular or Bimolecular Unimolecular or Bimolecular Cleavage PathwaysCleavage Pathways

R O RHX

R O R

H

+X-

SN

1

SN

2

R O R

H

+

R O R

H

+X-

ROHR+ X-

RX

RX ROH+

Protonation

Epoxide Ring OpeningEpoxide Ring OpeningEpoxide Ring OpeningEpoxide Ring Opening

Unimolecular or BimolecularUnimolecular or BimolecularUnimolecular or BimolecularUnimolecular or Bimolecular

OH

H

H

R

OH

H

H

R

1SN

SN

2

H+

ROH

OH

H

H

R

H

+ H

H

H

R

O

H

+ROH

RO

CR H

C HH

OHH+-

ROHRO- CH

O

R

CH2 ORH2O

CH

R

CH2 OR

OH