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Alcohols and Phenols
Alcohols and Phenols
AlcoholsandPhenols
AlcoholsandPhenols
AlcoholsandStu
1.Oxida9on
A.Alcoholtocarbonyl
2.Reduc9on
A.Carbonyltoalcohol
3.GrignardAddi9on
A.Addi9onofalkylgrouptocarbonyl
4.AlkylHalideSubs9tu9on
A.Subs9tu9onofalcoholbyhalide
5.Dehydra9onElimina9on
A.Elimina9onofalcoholtoformalkene
AlcoholsandPhenols
ReducingAgents
NaBH4
1.Doesnotinterferewithotherfunc9onal
groupsoutsideofketonesandaldehydes
LiAlH4
1.Doesnotreducedoublebonds(namely,alkenes)
outsideofaldehydes,ketones,carboxylicacidsand
esters.
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
Solvents:
1.Ethanol(forNaBH4)
2.Ether(forLiAlH4)
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
Solvents:
1.Ethanol(forNaBH4)
2.Ether(forLiAlH4)
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.WhenthreeofthegroupsaXachedtothealcoholcarbonaredierentitMUST
comefromaketone
2.IftwoofthegroupsaXachedtothealcoholcarbonarethesame,itmaycome
fromeitheraketoneoranester.
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,itmay
comefromeitheraketoneoranester.
2.Stereochemistry
AlcoholsandPhenols
Grignardaddi9onto:Carboxylicacids
Step1
1.
AlcoholsandPhenols
Grignardaddi9onto:Carboxylicacids
Step1
1.Itdoesntoccurbecausetheacidiccarboxylhydrogenreactswiththe
basisGrignardreagenttoyieldahydrocarbonandthemagnesiumsalt
oftheacid.
AlcoholsandPhenols
AlcoholtoAnion
Reactants
1.
2.
Products
1.
AlcoholsandPhenols
AlcoholtoAnion
Reactants
1.primary,secondaryorter9aryalcohol
2.NaH
Products
1.Na+O
AlcoholsandPhenols
GrignardLimita9ons
1.Grignardreagentcantbepreparedfromanorganohalideifother
reac9vefunc9onalgroupsarepresentinthesamemolecule.The
Grignardreagentwillbeprotonatedbythesefunc9onalgroups:
A.
B.
C.
D.
2.TheGrignardreagentaddstothesegroups
A.
B.
C.
D.
E.
F.
AlcoholsandPhenols
GrignardLimita9ons
1.Grignardreagentcantbepreparedfromanorganohalideifother
reac9vefunc9onalgroupsarepresentinthesamemolecule.The
Grignardreagentwillbeprotonatedbythesefunc9onalgroups:
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
Regiochemistry:
1.Markovnikov
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
Products:
1.Primaryorsecondaryalkylhalide
Regiochemistry:
1.Markovnikov
Notes:
1.ViaanSN2reac9on
AlcoholsandPhenols
AlkylHalidesfrom:Primary&Secondary
Alcohols(PartIII)
Reactants:
1.
2.
3.
Solvent:
1.
Products:
1.
Regiochemistry:
1.
AlcoholsandPhenols
AlkylHalidesfrom:Primary&Secondary
Alcohols(PartIII)
Reactants:
1.Primaryorsecondaryalcohol
2.HFor
3.(CH3CH2)2NSF3(Diethylaminosulfurtriuoride)
Solvent:
1.Pyridine
Products:
1.Primaryorsecondaryalkylhalide
Regiochemistry:
1.Markovnikov
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
Reac9onsofalcohols:Dehydra9on
Reactants:
1.Ter9aryalcohol
2.H3O+
3.H2SO4
Solvent
1.THF
Products:
1.Alkene
Note:
1.UsesanE1mechanism
2.Secondaryandprimaryalcoholsrequirehigherconcentra9onsof
acidandarethusveryharshenvironments
AlcoholsandPhenols
Reac9onsofalcohols:Dehydra9on
Reactants:
1.
2.
Solvent
1.
Intermediates:
1.
Products:
1.
Note:
1.
2.
AlcoholsandPhenols
Reac9onsofalcohols:Dehydra9on
Reactants:
1.Secondaryandter9aryalcohols
2.POCl3
Solvent
1.Pyridine
Intermediates:
1.Dichlorophosphate
Products:
1.Alkene
Note:
1.UsesanE2mechanism
2.An9periplanarrela9onshipisneededbetweentheAlcoholandthe
Hydrogenofthecarbonthatisformingthedoublebond(thisonlyapplies
torings).
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;ifheatisusedyoucans9llregeneratetheini9alalcoholbutwillalsodehydratevia
elimina9onanyotheralcoholspresentinthereac9on)
2.Althoughter9ary,theyundergoSN2reac9onsbecauseSibondsaremuchlongerthan
Cbonds.
3.TMSethersdontreactwith:
1.Oxida9on
2.Reduc9on
3.Grignardreagents