ORGANIC CHEMISTRY CHAPTER 4 structure ofmolecules

Rotationandrigidity

Alkene

It is infactpossible to inter
convertcisandtransalkenesbut itrequires considerableamount
ofenergy 260KJmot1
Onewaytobreakthe a bond is topromotean e fromthe aorbitaltotheN'torbital inthiscase
therewouldbeonee inthebonding aorbitalandoneintheantibonding atorbitalandhenceno overall
bonding

Theenergyrequiredto dothiscorrespondstolightintheUVregion ofthespectrum

ShiningUVlighton analkenecanbreakthe2bond butnotthe 6 bond andallowsrotationtooccur

Alkane

Notall orientationsaboutthe bondare equallyfavorable

Comparasion
ofethylene ethene and ethane
Organic chemistry Chapter5 organicreactions
whymoleculesgenerallydon'treactwitheachother
Aim whysometimesmolecules reactwitheachother
do
Howmolecularshapeandstructuredeterminereactivity
Inchemicalreactionselectronsmovefromfueltoemptyorbitals
andelectrophiles
Identifyingnucleophiles
Representingthemovement
ofelectronsinreactionsbycurlyarrows
chemicalreactions

Notallcollisionsbetweenmoleculesleadtochemicalchange
Reautionsoccuronly if apairofmoleculeshaveenoughenergytoovercomethesuperficialrepulsion
Theminimumenergyrequiredforareaction activationenergy

chargeattractionbringsmolecules
together
Amorecommoncauseoforganicreactionsisattractionbetween achargedreagentcacationoranionandan
organiccompoundthatarebothdipole
stableorganicanionsmoreusuallycarrytheir
negativechargeonanatomthatisnot
carbon onoxygenforexample asintheacetateion a13 coi

Itisn'tnecessaryforeitherreagenttobecharged

I
Orbitaloverlapbringsmoleculestogether

Tosummarizethesituation
Ingeneralmoleculesrepeleachotherandneedtoovercomeabarrierwithaminimumamountofactivationenergytoreact
Mostorganicreactionsinvolveinteractionsbetweenfullandemptyorbitals
Manybutnotall alsoinvolvechargeinteractionswhich helpovercomeelectronicrepulsion
someionicreactionsinvolvenothingbutchargeattraction

Reactionshappenwhenelectronsflowbetweenmolecules
 Mechanism ofthereaction thedetaileddescriptionofthepathwaytheelectronstake
themoleculeacceptselectrons
Electrophile

Nucleophile the
moleculedonateselectrons

on
Ndonatesbothelectronsforformingbond dativecovalentbond
fromoneatom
Dativecovalentbondisjustanordinary6bondwhoseelectronshappentocome

orbitaloverlapis essentialforsuccessfulreaction

Nobondforming

Thebestreactionsareonesinwhichtheenergiesoftheinteractingorbitalsaresimilarinenergy
Fora reactiontotakeplacemoleculesmust
overcometheir electronicrepulsionbychargeattractionand or orbitaloverlap

haveorbitalsofappropriateenergytointeract afilledorbitalonthenucleophileandanemptyorbitalonthe
electrophile
approachearnothersuch thattheseorbitalscanoverlaptoforma bondinginteraction
 Organic chemistry Chapter5 organicreactions
Nucleophiles andelectrophiles

wecanignoreourinteractionsbetweenpairsof
filledorbitals1bondingandantibonding cancelout
andpairsofunfilled orbitals
um
nucleophiles

andelectrophiles

Thebestnucleophileshavehighenergyoccupiedmolecularorbitals Homos
Thebestelectrophileshavelowenergyunoccupied molecularorbitalsCLUMOSI

Identifying a nucleophile
negatively charged
Nucleophiles

neutralspecieswithapairofe onHomo
Yostcommoni havenonbondinglone
pairofe
witha lonepair

paiszszpbzsz.ph s 1525450353p4

theirlonepairsareevenhigherenergyoccupyingorbitals
madeupof 3s and 3p atomicorbitals

Anionswhichhavelonepairs areoftengoodnucleophilestoo 1nucleophileswithanegativecharge

Thenegativechargecannotbeassigned
tooneofthe lonepairs inparticular

Negativecharges likethisactuallyrepresents apair electrons boththeextraelectronanditspartnerinthe

of
lonepair sowenormallywrite mechanismswithanarrowstarting onnegativecharge
 bonding a orbitals especially cdoublebonds
The common 2nucleophilesarealkenesandaromaticrings
only

6bondassociatedwith electropositiveatoms suchas Bisi orthemetalsalongwithCorH

The6orbitalgeneratedfromelectropositiveCandevenmoreelectropositive Li
ishighinenergy

Identifying an electrophile
Electrophiles are neutralor positivelychargedspecieswithanemptyatomicorbital1suchasthe
empty porbitalinborane or a lowenergy antibondingorbitalthatcaneasilyaccepte

Electrophiles withan emptyatomicorbital

InmostorganicelectrophilestheWMDsarelowenergyantibondingorbitalsassociatedwith
electronegative atoms Cat or 6
 with a doublebondto an electronegativeatom

1
zitislower
inenergythan
the6 orbital
withasinglebondtoan electronegativeatom in o

Some6bondsareelectrophiliceventheyhavenodipoleatall eg 7v Brzand42

Summary
Organic chemistry Chapter5 organicreactions
curlyarrows representreactionmechanisms
curlyarrowsshowthemovementofelectrons
Acurlyarrowrepresentsthemovementof apairofelectronsfromafilledorbitalintoanemptyorbital

weakbond
whenthenucleophileattacksanantibondingorbitalsuchas Br Brbondwehavejustbeendiscussing weneed
twoarrowsonetomakethenewbondandonetobreaktheold

AttackofabaseonthestrongacidHBr

of
Noticethatthefinalarrowendsupdeliveringtheelectronstoanelectronegativeatomsatisfyingitsdesire
electrondensityThisispart thereasonwhydoubleor singlebondstoelectronegativeatomsareoften a
of
featureofgoodelectrophiles

Curlyarrowsalwaysstartonsomethingrepresenting a pairof es
A negativecharge
Alonepair
Abond
andendatthepointthose es aremovingto

chargeisconserved in eachstepof a reaction

Ifthestartingmaterialsarechargedthentheproductsmusthaveoverallthesamecharge

1430
1 iselectrophilic at Handnot0
whena abondisbrokenratherthan6bond onlythe abond wasbrokenandthe6 bondshouldbe

leftinplace
Xbond as nucleophiles

or

withatom specific curlyarrow

Twoionsreactwitheachother

withempty porbital

6bondas nucleophiles

or
w
He
LUM0thea orbitaloftheCeodoublebond
an'tstartfrom0 as itdoesn'tpresenta lonepairall8 e aroundtheBatomareshownas 4 B H
bonds

Theantonwhichformsis an intermediate notthefinalproduct

LUMoi O H o
Organic chemistry Chapter5 organicreactions
Drawingyourownmechanismswithcurlyarrows

whenyoumeetmins 1 identitywhichbondshavebeen formedandbroken

2decidewhichmolecule isthenucleophileandwhichistheelectrophile
eg
drawout
allbondsinvolved

nucleophile lonepair p
electrophile bondbetween candelectronegativeelement2
v

watchoutforfivevalentcarbons
Mostatomsinstableorganicmolecules have afullcomplementofneutrons twointhecaseofH eight
inthecasesofC Nando
so ifyoumake anewbondyoumustalsobreakanexistingbond

B c N oneverhave morethan 4 bonds Ifyoumakea newbondtounchargedH C Nor0you

mustalsobreakoneoftheexistingbondsinthesamestep
Mechanisms withseveralsteps

I
notreallytheproduct

t
e.g primaryalcohols canbeconvertedintosymmetrical others inacidsolution

theavidmustdosth
t hastobeelectrophile
f
t
b

eg

stepbystepguidetodrawmechanismswithcurlyarrows
Drawoutthereagentsasclearstructuresfollowingtheguidelinesin or
Inspectthestartingmaterialsandproducts andassesswhathashappened inthereaction
mostnucleophilic then
moleculesanddecidewhichisthe
Identifythenucleophiliccentres inallthereactant
identifyelectrophiliccentres
Drawcurlyarrowfromthenucleophiletotheelectrophile
considerwhetheranyatomthathasbeenchangednowhas
toomanybonds
writeoutthestructureoftheproductsspecifiedbythecurlyarrows
Repeat4 6 asrequiredtoproduceastableproduct
 Organicchemistry Chapter6 addition tothecarbonylgroup
Nucleophilic

Howandwhythe o groupreactswith
nucleophiles
molecularorbitalsandcurlyarrows
Atm Explainingthereactivity ofthe ogroupusing
whatsorts molecules canbemadebyreactions of G ogroup
of
Howacid orbasecatalystsimprovetheactivityofthe ogroup

Molecularorbitalsexplainthereactivity ofthecarbonylgroup
Narnthis
04 TO alcohol
Huo W 78 yield

No 017 9 to noTO T H protonation

addition
nucleophilic additionsto carbonylgroups
ofan tothe t isthegeneralfeatureofannucleophilic
carbonylgroup

Additionstocarbonylgroupgeneraly consist
oftwomechanisticsteps
nucleophilic attack onthecarbonyl
group
Protonation
of theanionthatresults

planar Thepolarizationin a
bondmeans it is
skew towardsoxygen
becauseoxygen ismore
electronegativethanC

converselythe unfilled
atantibondingorbital
isskewedintheopposite
direction

whyc o is soreactive IEvenshorterandwithhigherenergythec o

polarization
Thepolarizedo_0bondgivesthecarbonatomsomedegreeofpositivechargeandthisattractsthenegativecharge
ofnucleophiles likecyanide
Thepolarizationof at antibondingorbitaltowardsC LUMO
CN HOMO is an SPorbital oncarbon
Organicchemistry Chapter6 Nucleophilic addition tothecarbonylgroup

Attackofcyanideonaldehydesandketones

Nam Nc on
KTH HaoHu k H
orbitalsofthecyanide ion aldehyde product cyanohydrin

I
N C0 f
0
ENT119 N THto
KAH R H

cyanohydrinsin synthesis

cyanohydrinformation isreversiblejustdissolvinga cyanohydrininwatercangivebackthealdehyde orketoneyou

startedwith anaqueousbaseusuallydecomposed cyanohydrins completely
cyanide is agoodleavinggroup

Ho on
rA r poke on
ketone
cyanohydrin
a
no9 o un
t e l
od
n un
ri on
f r r r
cyanohydrinformation favorablefor
is anequilibriumbetweenstartingmaterialsandproducts theequilibrium ismore
attachedtothecarbonyl atom
carbon
aldehydecyanohydrinthan forketonecyanohydrinsduetothesizeofthegroups

sterichindrance
from
thatresult
Effects thesize ofsubstituentsandtherepulsionbetweenthemarecalledstericeffectsandwecallthe
bylargesubstituentssterichindrance
forceexperienced
repulsive

Itaffectsreactionratesbutalsomakemoleculesreactbycompletelydifferentmechanisms
 Organicchemistry Chapter6 Nucleophilic addition tothecarbonylgroup
Theangleofnucleophilicattackon aldehydesandketones
carbon buttheyalsoalwaysapproachfrom a
Nucleophilesnotonlyalwaysattackcarbonylgroupat
particularangle

atdoesnothaveparallelatomicorbitalsasthere is a nodehalfwaydownthebondsotheatomic
orbitalsarealready at anangleThenucleophilesattackalongtheaxisofthelargerorbitalintheHOMO

by hydride on aldehydesandketones
Nucleophilicattack

hydrideion H whichispresentinthesalt Nan hassucha highchargedensitythat itonlyreacts

asbase Itsfilled isorbitalis ofidealsizetoreactwithhydrogenatom'scontributiontothe s
orbitalof an H Xbond xcanbeanyatom butmuchtoosmalltointeracteasilywithcarbon'smore
diffuse zporbitalcontributiontotheLUMOCat oftheCeogroup

aBH4 l BE
H t H
borohydrideanion

I
 Theoxyanionproducedcanhelpwithstabilizingtheelectron deficientBHzmoleculebyadding
toitsemptyporbital Thenewtetravalentboroncantransferasecond Hatom withitspairof
ofaldehyde
electrons toanothermolecule

Examples ofreductionswithsodiumborohydride

Thewateroralcoholsolventprovides
theprotonneededtoformthe
fromthealkoxide
alcohol

sodiumborohydride isoneofthe weakerhydridedoners More powerfulone LiAlHq

canbeusedinwater reactviolently
withwater
Examplesofredution
 Organicchemistry Chapter6 Nucleophilic addition tothecarbonylgroup
Theangleofnucleophilicattackon aldehydesandketones
carbon buttheyalsoalwaysapproachfrom a
Nucleophilesnotonlyalwaysattackcarbonylgroupat
particularangle

atdoesnothaveparallelatomicorbitalsasthere is a nodehalfwaydownthebondsotheatomic
orbitalsarealready at anangleThenucleophilesattackalongtheaxisofthelargerorbitalintheHOMO

by hydride on aldehydesandketones
Nucleophilicattack

hydrideion H whichispresentinthesalt Nan hassucha highchargedensitythat itonlyreacts

asbase Itsfilled isorbitalis ofidealsizetoreactwithhydrogenatom'scontributiontothe s
orbitalof an H Xbond xcanbeanyatom butmuchtoosmalltointeracteasilywithcarbon'smore
diffuse zporbitalcontributiontotheLUMOCat oftheCeogroup

aBH4 l BE
H t H
borohydrideanion

I
Organicchemistry Chapter6 Nucleophilic addition tothecarbonylgroup

Additionofwatertoaldehydesandketones

tHuo H H
µ r
f
expert13C
HT H
signal Bcsignalat
between Isozoo
ppm 83ppm
t Huo
on
pfkp K R
of
significantconcentrations hydrateare
generally
formedonlyfromaldehydes

no
a O_0 o H oH
Hidy II y two H O
a HowX
H
X
on
H H H H H H
attack
Formaldehyde is anextremelyreactivealdehydesas ithasno substituentstohinder

atstericeffect
stericandelectroniceffects
stericeffectsare concernedwiththesizeandshapeofgroupswithinmolecules
fromthewaythat electronegativity differencebetweenatomsaffecttheway
Electroniceffects result
electrons are distributed inmolecules Theycan bedividedintoinductiveeffects whichare consequence

ofthewaythatelectronegativity differencesleadto polarizationof 6 bonds andconjugation1

sometimes
calledmesomericeffect TattakixFKWhichaffectsthedistribution electrons in a bond
of
stericandelectroniceffectsare two ofthemainfactors dominatingthereactivityofnucleophilesand
electrophiles

ThelargerK themorethe
equilibrium is to theright

Thesamestructuralfeaturesthatfavour ordisfavourhydrateformationare
importantindeterminingthereactivityofcarbonylcompoundswithothernucleophiles
whethertheruinsarereversibleornot
Sterichinderanceandmorealkylsubstituentsmakecarbonylcompoundslessreactive
electronwithdrawinggroups andsmallringsmakesthemmorereactive
7morefavorableangleforthreememberedring