StructuresofAldehydesandKetones

Bothaldehydesandketonescontainacarbonylgroup
AldehydeshaveatleastoneHattached,whileketoneshave
twoCsattachedtothecarbonyl
AcarbonylconsistsofaCdoublebondedtoanO
Likeinanalkene,thedoublebondconsistsofonesigmaand
onepibond
Thecarbonylisaverypolargroup
OismoreelectronegativethanC,soCObondsarepolar
Also,thecarbonylhastworesonanceforms
Thispolaritymakescarbonylschemicallyreactive

NamingKetones

Parentnameendsinone
Findlongestchaincontainingthecarbonylgroup
NumberCsstartingatendnearestcarbonylgroup
Locateandnumbersubstituentsandgivefullname
useanumbertoindicatepositionofcarbonylgroup
cyclicketoneshavecyclobeforetheparentname;
numberingbeginsatthecarbonylgroup,goingindirection
thatgivessubstituentslowestpossiblenumbers
useaprefix(di,tri)toindicatemultiplecarbonylgroupsin
acompound

NamingAldehydes

Parentnameendsinal
Findlongestchaincontainingthecarbonylgroup
NumberCsstartingatendnearestcarbonylgroup
Locateandnumbersubstituentsandgivefullname
aldehydestakeprecedenceoverketonesandalcoholsinnaming
ketonesarecalledoxoasasecondarygroup
alcoholsarecalledhydroxyasasecondarygroup
thesmallestaldehydesareusuallynamedwithcommonnames
wewillnotnamecyclicaldehydes(exceptbenzaldehyde)

PhysicalPropertiesofAldehydesandKetones
Becausethecarbonylgroupispolar,aldehydesandketones
havehigherboilingpointsthanhydrocarbons
However,theyhavenoHattachedtotheO,sodonothave
hydrogenbonding,andhavelowerboilingpointsthanalcohols
Likeethers,aldehydesandketonescanhydrogenbondwith
water,sothosewithlessthan5carbonsaregenerallysolublein
water
Aldehydesandketonescanbeflammableand/ortoxic,though
generallynothighlyso
Theyusuallyhavestrongodors,andareoftenusedas
flavoringsorscents

OxidationofAldehydes
Recallthataldehydesandketonesareformedbytheoxidationof
primaryandsecondaryalcohols,respectively
Alsorecallthataldehydesarereadilyoxidizedtocarboxylic
acids,butketonesarenot
Tollensreagent(silvernitrateplusammonia)canbeusedto
distinguishbetweenketonesandaldehydes
withaldehydestheAg2+isreducedtoelementalsilver,which
formsamirrorlikecoatonthereactioncontainer
Sugars(likeglucose)oftencontainahydroxygroupadjacentto
analdehyde
Benedictsreagent(CuSO4)canbeusedtotestforthistypeof
aldehyde;theblueCu2+formsCu2O,aredsolid

ReductionofAldehydesandKetones
ReductioncanbedefinedasalossinbondstoOoragainin
bondstoH
Aldehydesandketonescanbereducedtoformalcohols
Aldehydesformprimaryalcohols
ketonesformsecondaryalcohols
Manydifferentreducingagentscanbeused,includingH 2,LiAlH4
(lithiumaluminumhydride)andNaBH4(sodiumborohydride)
However,NaBH4isusuallythereagentofchoice
hydrogenationwillalsoreducealkenesandalkynesifpresent
LiAlH4ismorereactivethanNaBH4,butreactsviolentlywith
waterandexplodeswhenheatedabove120C

AdditionofWatertoAldehydesandKetones
H2Ocanaddacrossthecarbonylofanaldehydeoraketone,
similartotheadditionofH2Otoanalkene
ApartialpositiveHfromwaterbondstothepartialnegative
carbonylO,andthepartialnegativeOfromwaterbondstothe
partialpositivecarbonylC
Theproductofthisreversiblereactionisahydrate(a1,1diol)
Ingeneral,theequilibriumfavorsthecarbonylcompound,butfor
somesmallaldehydesthehydrateisfavored
Thereactioncanbecatalyzedbyeitheracidorbase

MechanismofAcidCatalyzedHydrationofFormaldehyde
First,thecarbonylOisprotonatedbytheacidcatalyst
Next,H2Oattacksthecarbonylcarbontoformaprotonatedhydrate
Finally,H2Oremovestheprotontoformthehydrate

AdditionofAlcoholstoAldehydesandKetones
Alcoholscanaddtoaldehydesandketonesusinganacidcatalyst
Additionof2alcoholsproducesanacetal(adiether)
Thereactionintermediate,afteradditionofonealcohol,isa
hemiacetal(notusuallyisolated)
Thisisareversiblereaction
removalofH2Ofavorsacetal
additionofH2Ofavorsaldehydeorketone
Acetalsareoftenusedasprotectinggroupsinorganicsynthesis

FormationofCyclicHemiacetals
Whenanaldehydeoraketoneisinthesamemoleculeasan
alcohol,acyclichemiacetalcanform
Thesearemorestablethanthenoncycliconesandcanbe
isolated
Sugars,likeglucoseandfructose,existprimarilyinthecyclic
hemiacetalform
Whenanalcoholaddstoacyclichemiacetal,acyclicacetalis
formed(thisishowsugarsbondtogetherinpolysaccharides)

Stereoisomers
Recallthatconstitutionalisomershavethesamemolecular
formula,buttheatomsarebondedinadifferentorder
Stereoisomershavethesamemolecularformula,andthe
samebondingorder,buttheatomsarearrangeddifferently
in3Dspace
Therearetwotypesofstereoisomers:
enantiomersarenonsuperimposablemirrorimages
diasteriomersarestereoisomersthatarenotmirror
images(cistransisomersatypeofdiastereomers)

Chirality
Anobject,oramolecule,ischiralifithasamirrorimage
thatisnotsuperimposable
Themostfamiliarchiralobjectsareyourhands
therighthandisthemirrorimageofthelefthand
nomatterhowyouturnthem,theycantbesuperimposed
Manyorganiccompoundsarealsochiral
mostbiomolecules(aminoacids,sugars,etc.)arechiral
andusuallyonlyoneofthestereoisomersisused
Inorderforacarboninanorganiccompoundtobechiral,
itmusthave4differentgroupsattached(otherwisethe
mirrorimagewillbesuperimposable)

FischerProjections
Fischerprojectionsareasimplewaytorepresentchiral
molecules(especiallysugars)
Thebondstoachiralcarbonareshownascrossed
perpendicularlines,withthechiralCatthecenter
Horizontalbondsarecomingtowardsyou(likewedges)
Verticalbondsaregoingawayfromyou(likedashes)
TheDandLclassificationofsugarsisbasedonthe
simplestsugar,glyceraldehyde
Compoundswithmorethanonechiralcarbon,suchas
largersugars,canalsoberepresentedasFischer
projections
Eachplacewhereahorizontallinecrossesthevertical
linerepresentsacarbon