Alcohols and Phenols

Chapter17AlcoholsandPhenols

AlcoholsandPhenols

AlcoholsandStu1.Oxida9on

A.Alcoholtocarbonyl2.Reduc9on

A.Carbonyltoalcohol3.GrignardAddi9on

A.Addi9onofalkylgrouptocarbonyl4.AlkylHalideSubs9tu9on

A.Subs9tu9onofalcoholbyhalide5.Dehydra9onElimina9on

A.Elimina9onofalcoholtoformalkene

AlcoholsandPhenols

ReducingAgentsNaBH41.Doesnotinterferewithotherfunc9onalgroupsoutsideofketonesandaldehydes

LiAlH41.Doesnotreducedoublebonds(namely,alkenes)outsideofaldehydes,ketones,carboxylicacidsandesters.

AlcoholsandPhenols

Reduc9onofAldehydes Step1

Reactants: 1.or 2.

Solvents: 1. 2.

Step2: Reactants

1. Products:

1.

AlcoholsandPhenols

Reduc9onofAldehydes Step1

Reactants: 1.NaBH4orLiAlH4 2.Aldehyde

Solvents: 1.Ethanol(forNaBH4) 2.Ether(forLiAlH4)

Step2: Reactants

1.H3O+ Products:

1.Primaryalcohol

AlcoholsandPhenols

Reduc9onofKetones Step1

Reactants: 1.or 2.

Solvents: 1. 2.

Step2: Reactants

1. Products:

1.

AlcoholsandPhenols

Reduc9onofKetones Step1

Reactants: 1.NaBH4orLiAlH4 2.Ketone


Step2: Reactants

1.H3O+ Products:

1.Secondaryalcohol

AlcoholsandPhenols

Reduc9onofEsters Step1

Reactants: 1.or 2.

Solvents: 1. 2.

Step2: Reactants

1. Products:

1. Note:

1.

AlcoholsandPhenols

Reduc9onofEsters Step1

Reactants: 1.NaBH4orLiAlH4 2.Ester


Step2: Reactants

1.H3O+ Products:

1.Primaryalcohol Note:

1.NaBH4reducesestersveryslowly

AlcoholsandPhenols

Reduc9onofCarboxylicacids Step1

Reactants: 1. 2.

Solvents: 1.

Step2: Reactants

1. Products:

1. Note:

1.

AlcoholsandPhenols

Reduc9onofCarboxylicacids Step1

Reactants: 1.LiAlH4 2.Carboxylicacid

Solvents: 1.Ether(forLiAlH4)

Step2: Reactants

1.H3O+ Products:

1.Primaryalcohol Note:

1.NaBH4doesnotreducecarboxylicacidsatall

AlcoholsandPhenols

Grignardaddi9onto:Formaldehyde Step1

Reactants: 1. 2.

Solvents: 1.

Step2: Reactants

1. Products:

1.

AlcoholsandPhenols

Grignardaddi9onto:Formaldehyde Step1

Reactants: 1.Formaldehyde 2.RMgBr

Solvents: 1.Ether

Step2: Reactants

1.H3O+ Products:

1.Primaryalcohol 2.Stereochemistry

AlcoholsandPhenols

Grignardaddi9onto:Aldehyde Step1

Reactants: 1. 2.

Solvents: 1.

Step2: Reactants

1. Products:

1. 2.

AlcoholsandPhenols

Grignardaddi9onto:Aldehyde Step1

Reactants: 1.Aldehyde 2.RMgBr

Solvents: 1.Ether

Step2: Reactants

1.H3O+ Products:

1.Secondaryalcohol 2.Stereochemistry

AlcoholsandPhenols

Grignardaddi9onto:Ketone Step1

Reactants: 1. 2.

Solvents: 1.

Step2: Reactants

1. Products:

1. Note:

1. 2. 3.

AlcoholsandPhenols

Grignardaddi9onto:Ketone Step1

Reactants: 1.Ketone 2.RMgBr

Solvents: 1.Ether

Step2: Reactants

1.H3O+ Products:

1.Ter9aryalcohol Note:

1.WhenthreeofthegroupsaXachedtothealcoholcarbonaredierentitMUSTcomefromaketone

2.IftwoofthegroupsaXachedtothealcoholcarbonarethesame,itmaycomefromeitheraketoneoranester.

3.Stereochemistry

AlcoholsandPhenols

Grignardaddi9onto:Ester Step1

Reactants: 1. 2.

Solvents: 1.

Step2: Reactants

1. Products:

1. Notes

1. 2.

AlcoholsandPhenols

Grignardaddi9onto:Ester Step1

Reactants: 1.Ester 2.RMgBr

Solvents: 1.Ether

Step2: Reactants

1.H3O+ Products:

1.Ter9aryalcohol Notes

1.IftwoofthegroupsaXachedtothealcoholcarbonarethesame,itmaycomefromeitheraketoneoranester.

2.Stereochemistry

AlcoholsandPhenols

Grignardaddi9onto:Carboxylicacids Step1

1.

AlcoholsandPhenols

Grignardaddi9onto:Carboxylicacids Step1

1.ItdoesntoccurbecausetheacidiccarboxylhydrogenreactswiththebasisGrignardreagenttoyieldahydrocarbonandthemagnesiumsaltoftheacid.

AlcoholsandPhenols

AlcoholtoAnion Reactants

1. 2.

Products 1.

AlcoholsandPhenols

AlcoholtoAnion Reactants

1.primary,secondaryorter9aryalcohol 2.NaH

Products 1.Na+O

AlcoholsandPhenols

GrignardLimita9ons 1.Grignardreagentcantbepreparedfromanorganohalideifotherreac9vefunc9onalgroupsarepresentinthesamemolecule.TheGrignardreagentwillbeprotonatedbythesefunc9onalgroups: A. B. C. D.

2.TheGrignardreagentaddstothesegroups A. B. C. D. E. F.

AlcoholsandPhenols

GrignardLimita9ons 1.Grignardreagentcantbepreparedfromanorganohalideifotherreac9vefunc9onalgroupsarepresentinthesamemolecule.TheGrignardreagentwillbeprotonatedbythesefunc9onalgroups: A.OH(hydroxyl) B.NH C.SH(Thiol) D.CO2H(Carboxylicacid)

2.TheGrignardreagentaddstothesegroups A.HC=O(aldehyde) B.RC=O(ketone) C.NR2C=O(Amide) D.C#N(Nitrile) E.NO2(Nitrogroup) F.SO2R(Thioester)

AlcoholsandPhenols AlkylHalidesfrom:TerHaryAlcohols

Reactants: 1. 2.

Solvent: 1.

Temperature: 1.

Products: 1.

Regiochemistry: 1.

Notes: 1. 2.

AlcoholsandPhenols AlkylHalidesfrom:TerHaryAlcohols

Reactants: 1.Ter9aryalcohol 2.HX(gas)

Solvent: 1.Ether

Temperature: 1.0C

Products: 1.Ter9aryalkylhalide

Regiochemistry: 1.Markovnikov

Notes: 1.Reac9vityorder:3>2>1 2.ViaanSN1reac9on

AlcoholsandPhenols AlkylHalidesfrom:Primary&SecondaryAlcohols(PartI)

Reactants: 1. 2.

Solvent: 1. 2.

Intermediates: 1.

Products: 1.

Regiochemistry: 1.

Notes: 1.

AlcoholsandPhenols AlkylHalidesfrom:Primary&SecondaryAlcohols(PartI)

Reactants: 1.Primaryorsecondaryalcohol 2.SOCl2(Thionylchloride)

Solvent: 1.Pyridineor 2.Et3N

Intermediates: 1.Chlorosulte

Products: 1.Primaryorsecondaryalkylhalide


Notes: 1.ViaanSN2reac9on

AlcoholsandPhenols AlkylHalidesfrom:Primary&SecondaryAlcohols(PartII)

Reactants: 1. 2.

Solvent: 1. 2.

Intermediates: 1.

Products: 1.

Regiochemistry: 1.

Notes: 1.

AlcoholsandPhenols

AlkylHalidesfrom:Primary&SecondaryAlcohols(PartII) Reactants:

1.Primaryorsecondaryalcohol 2.PBr3(Phosphoroustribromide)

Solvent: 1.Ether

Intermediates: 1.Dibromophosphite

Temperature: 1.35C



Notes: 1.ViaanSN2reac9on

AlcoholsandPhenols

AlkylHalidesfrom:Primary&SecondaryAlcohols(PartIII) Reactants:

1. 2. 3.

Solvent: 1.

Products: 1.

Regiochemistry: 1.

AlcoholsandPhenols

AlkylHalidesfrom:Primary&SecondaryAlcohols(PartIII) Reactants:

1.Primaryorsecondaryalcohol 2.HFor 3.(CH3CH2)2NSF3(Diethylaminosulfurtriuoride)

Solvent: 1.Pyridine



AlcoholsandPhenols

ConversionofalcoholstoTosylates Step1

Reactants 1. 2.

Solvent: 1.

Step2: Reactants:

1. 2.

Product 1.

Notes 1. 2.

AlcoholsandPhenols

ConversionofalcoholstoTosylates Step1

Reactants 1.(S)Alcohol 2.Tosylate

Solvent: 1.Pyridine

Step2: Reactants:

1.(S)Tosylatecomplex 2.Alkoxide

Product 1.(R)Ether

Notes 1.Tosylateshaveoneinversionofstereochemistryoverall 2.Alkylhalideshavetwoinversionsofstereochemistry,zerooverall

AlcoholsandPhenols

Reac9onsofalcohols:Dehydra9on Reactants:

1. 2. 3.

Solvent 1.

Products: 1.

Note: 1. 2.

AlcoholsandPhenols


1.Ter9aryalcohol 2.H3O+ 3.H2SO4

Solvent 1.THF

Products: 1.Alkene

Note: 1.UsesanE1mechanism 2.Secondaryandprimaryalcoholsrequirehigherconcentra9onsofacidandarethusveryharshenvironments

AlcoholsandPhenols


1. 2.

Solvent 1.

Intermediates: 1.

Products: 1.

Note: 1. 2.

AlcoholsandPhenols


1.Secondaryandter9aryalcohols 2.POCl3

Solvent 1.Pyridine

Intermediates: 1.Dichlorophosphate

Products: 1.Alkene

Note: 1.UsesanE2mechanism 2.An9periplanarrela9onshipisneededbetweentheAlcoholandtheHydrogenofthecarbonthatisformingthedoublebond(thisonlyappliestorings).

AlcoholsandPhenols

Oxida9on:PrimaryAlcohol Reactants:

1. 2.or 3.or 4.or 5.

Products: 1.

Note: 1. 2.

AlcoholsandPhenols

Oxida9on:PrimaryAlcohol Reactants:

1.Primaryalcohol 2.KMnO4or 3.CrO3(inH3O+andacetone)or 4.Na2Cr2O7(InH2O,CH3CO2H,heat)or 5.C5H6NCrO3Cl(akaPCC)

Products: 1.Aldehyde,whichwillproceedtocarboxylicacid(unstoppable)

Note: 1.Ter9arydoesnotreactwiththethreeabovemen9onedoxidants 2.NeitherdoesBenzyne

AlcoholsandPhenols

Oxida9on:PrimaryAlcohols Reactants:

1. 2.or 3.

Solvent 1.

Products: 1.

AlcoholsandPhenols

Oxida9on:PrimaryAlcohols Reactants:

1.Primaryalcohol 2.DessMar9nperiodinaneor 3.PCC

Solvent 1.CH2Cl2

Products: 1.Aldehyde

AlcoholsandPhenols

Oxida9on:SecondaryAlcohol Reactants:

1. 2.or 3.or 4. 5.

Products: 1.

Note: 1.

AlcoholsandPhenols

Oxida9on:SecondaryAlcohol Reactants:

1.Secondaryalcohol 2.KMnO4or 3.CrO3(inH3O+andacetone)or 4.Na2Cr2O7(InH2O,CH3CO2,heat) 5.C5H6NCrO3Cl(akaPCC)

Products: 1.Ketone

Note: 1.Ter9arydoesnotreactwiththethreeabovemen9onedoxidants

AlcoholsandPhenols

Oxida9on:SecondaryAlcohols Reactants:

1. 2.or 3.

Solvent 1.

Products: 1.

AlcoholsandPhenols

Oxida9on:SecondaryAlcohols Reactants:

1.Secondaryalcohol 2.DessMar9nperiodinane 3.PCC

Solvent 1.CH2Cl2

Products: 1.Ketone

AlcoholsandPhenols

Oxida9on:CarboxylicacidstoEsters Reactants:

1. 2.

Solvent 1. 2.

Products: 1.

AlcoholsandPhenols

Oxida9on:CarboxylicacidstoEsters Reactants:

1.Benzoicacid 2.Methanol

Solvent 1.HCl 2.Heat

Products: 1.MethylBenzoate

AlcoholsandPhenols

Oxida9onofPhenols Reactants:

1. 2.or 3.

Solvent 1.

Products: 1.

AlcoholsandPhenols

Oxida9onofPhenols Reactants:

1.Phenol 2.Na2Cr2O7(InH2O,CH3CO2,heat)or 3.(KSO3)2NO(akaFremysSalt)

Solvent 1.H2O

Products: 1.Benzoquinone(1,4dicyclohexanone)

AlcoholsandPhenols

RedoxofBenzoquinone Reactants:

1. 2.or 3.

Products: 1.

AlcoholsandPhenols

RedoxofBenzoquinone Reactants:

1.Benzoquinone 2.SnCl2,H2Oor 3.NaBH4

Products: 1.Hydroquinone(pdihydroxybenzene)

AlcoholsandPhenols

Protec9onofAlcohols Reactants:

1. 2.

Intermediate: 1.

Solvent 1.

Products: 1.

Note: 1. 2. 3.

1. 2. 3.

AlcoholsandPhenols

Protec9onofAlcohols Reactants:

1.Alcohols 2.ClSi(CH3)3(chlorotrimethylsilane)

Intermediate 1.ROSiR3(trimethylsilylether)

Solvent 1.N(CH2CH3)3(Triethylamine)

Products: 1.NormallyaGrignardreagentreactedalcohol

Note: 1.TMSethersreactwithuorideionoraqueousacidtoregeneratetheini9alalcohol(no

heat;ifheatisusedyoucans9llregeneratetheini9alalcoholbutwillalsodehydrateviaelimina9onanyotheralcoholspresentinthereac9on)

2.Althoughter9ary,theyundergoSN2reac9onsbecauseSibondsaremuchlongerthanCbonds.

3.TMSethersdontreactwith: 1.Oxida9on 2.Reduc9on 3.Grignardreagents

Alcohols and Phenols

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