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ChemWiki:TheDynamicChemistryHypertext>Core>OrganicChemistry>Reactions>SubstitutionReactions>SN1>EffectsofSolvent,
LeavingGroup,andNucleophileonUnimolecularSubstitution

Effects of Solvent, Leaving Group, and Nucleophile on

Unimolecular Substitution

Just as with SN2 reactions, the nucleophile, solvent and leaving group also affect SN1 (Unimolecular Nucleophilic Substitution) reactions. Polar
proticsolventshaveahydrogenatomattachedtoanelectronegativeatomsothehydrogenishighlypolarized.Polaraproticsolventshaveadipole
moment,buttheirhydrogenisnothighlypolarized.PolaraproticsolventsarenotusedinSN1reactionsbecausesomeofthemcanreactwiththe
carbocationintermediateandgiveyouanunwantedproduct.Rather,polarproticsolventsarepreferred.

Introduction
Sincethehydrogenatominapolarproticsolventishighlypositivelycharged,itcaninteractwiththeanionicnucleophilewhichwouldnegatively
affect an SN2, but it does not affect an SN1 reaction because the nucleophile is not a part of the ratedetermining step (See SN2 Nucleophile).
Polar protic solvents actually speed up the rate of the unimolecular substitution reaction because the large dipole moment of the solvent helps to
stabilizethetransitionstate.Thehighlypositiveandhighlynegativepartsinteractwiththesubstratetolowertheenergyofthetransitionstate.Since
thecarbocationisunstable,anythingthatcanstabilizethisevenalittlewillspeedupthereaction.

Sometimes in an SN1 reaction the solvent acts as the nucleophile.This is called a solvolysis reaction (see example below).The polarity and the
abilityofthesolventtostabilizetheintermediatecarbocationisveryimportantasshownbytherelativeratedataforthesolvolysis(seetablebelow).
Thedielectricconstantofasolventroughlyprovidesameasureofthesolvent'spolarity.Adielectricconstantbelow15isusuallyconsiderednon
polar.Basically,thedielectricconstantcanbethoughtofasthesolvent'sabilitytoreducetheinternalchargeofthesolvent.Soforourpurposes,the
higherthedielectricconstantthemorepolarthesubstanceandinthecaseofSN1reactions,thefastertherate.

Belowisthesamereactionconductedintwodifferentsolventsandtherelativeratethatcorrespondswithit.

ThefigurebelowshowsthemechanismofanSN1 reaction of an alkyl halide with water. Since water is also the solvent, this is an example of a
solvolysisreaction.

Examplesofpolarproticsolventsare:aceticacid,isopropanol,ethanol,methanol,formicacid,water,etc.

Effects of Nucleophile
The strength of the nucleophile does not affect the reaction rate of SN1 because, as stated above, the nucleophile is not involved in the rate
determiningstep.However,ifyouhavemorethanonenucleophilecompetingtobondtothecarbocation,thestrengthsandconcentrationsofthose
nucleophilesaffectsthedistributionofproductsthatyouwillget.Forexample,ifyouhave(CH3)3CClreactinginwaterandformicacidwherethe
waterandformicacidarecompetingnucleophiles,youwillgettwodifferentproducts:(CH3)3COHand(CH3)3COCOH.Therelativeyieldsofthese
productsdependontheconcentrationsandrelativereactivitiesofthenucleophiles.

Effects of Leaving Group

AnSN1reactionspeedsupwithagoodleavinggroup.Thisisbecausetheleavinggroupisinvolvedin
theratedeterminingstep.AgoodleavinggroupwantstoleavesoitbreakstheCLeavingGroupbond
faster.Oncethebondbreaks,thecarbocationisformedandthefasterthecarbocationisformed,thefaster
thenucleophilecancomeinandthefasterthereactionwillbecompleted.
A good leaving group is a weak base because weak bases can hold the charge.They're happy to leave
with both electrons and in order for the leaving group to leave, it needs to be able to accept electrons.
Strongbases,ontheotherhand,donateelectronswhichiswhytheycan'tbegoodleavinggroups.Asyou
gofromlefttorightontheperiodictable,electrondonatingabilitydecreasesandthusabilitytobeagood
leaving group increases. Halides are an example of a good leaving group whos leavinggroup ability
increasesasyougodownthecolumn.

Thetworeactionsbelowisthesamereactiondonewithtwodifferentleavinggroups.Oneissignificantly
faster than the other. This is because the better leaving group leaves faster and thus the reaction can
proceedfaster.

Otherexamplesofgoodleavinggroupsaresulfurderivativessuchasmethylsulfateionandothersulfonateions(SeeFigurebelow)

MethylSulfateIonMesylateIonTriflateIonTosylateIon

References
UggerudE."Reactivitytrendsandstereospecificityinnucleophilicsubstitutionreactions."J.Phys.Org.Chem.200619461466.
Vollhardt,K.PeterC.,andNeilE.Schore.OrganicChemistryStructureandFunction.NewYork:W.H.Freeman,2007.
Petrucci,RalphH.GeneralChemistry:PrinciplesandModernApplications.UpperSaddleRiver,NJ:PearsonEducation,2007.
Suggs,WilliamJ.OrganicChemistry.Canada:Barron'sEducationalSeriesInc.,2002.

Outside Links

Outside Links
http://en.wikipedia.org/wiki/Sn1
http://www.youtube.com/watch?v=FuFpjx_ZeT0(PrettygoodsummaryofSN1reaction)

Problems
1.Putthefollowingleavinggroupsinorderofdecreasingleavinggroupability

2.WhichsolventwouldanSN1reactionoccurfasterin?H2OorCH3CN
3.WhatkindofconditionsdisfavorSN1reactions?
4.WhataretheproductsofthefollowingreactionanddoesitproceedviaSN1orSN2?

5.Howcouldyouchangethereactantsintheproblem4tofavortheothersubstitutionreaction?
6.IndicatetheexpectedproductandlistwhyitoccursthroughSN1insteadofSN2?

Answers

1.
2.AnSN1reactionwouldoccurfasterinH2Obecauseit'spolarproticandwouldstailizethecarbocationandCH3CNispolaraprotic.
3.Polaraproticsolvents,aweakleavinggroupandprimarysubstratesdisfavorSN1reactions.

4.
ReactionproceedsviaSN1becauseatertiarycarbocationwasformed,thesolventispolarproticandBrisagoodleavinggroup.
5.YoucouldchangethesolventtosomethingpolaraproticlikeCH3CNorDMSOandyoucoulduseabetterbaseforanucleophilesuchasNH2or
OH.

6.
ThisreactionoccursviaSN1becauseClisagoodleavinggroupandthesolventispolarprotic.Thisisanexampleofasolvolysisreactionbecause
thenucleophileisalsothesolvent.

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