AlexaBrown

CHM238Lab
TA:PatrickWallace
Monday2:30pm

Synthesisof2AcetylcyclohexanonethroughEnamineReactions

Thepurposeofthisexperimentwastosynthesize2acetylcyclohexanonethroughenamine
reactions.Distillation,reflux,extraction,columnchromatographywereusedtocarryoutthe
experiment.Theinfraredspectroscopy(IR)wasusedtoidentifythefinalproductandtestits
purity.TheIRshowedtheproducttohave sp2C H bonds, sp3C H bonds,and sp2C sp2O
bonds.Thepercentyieldwas303%.Thedatasuggeststhat2acetylcyclohexanonewasnot
successfullysynthesized.

Introduction
:

Thepurposeofthefirstweekwastocreateanenamine.Theenamineiscreatedby
addinganitrogennucleophiletoacarbonylcompoundfollowedbyelimination
(Trakanrungroj,2015).Inthecaseofthislab,thatispyrrolidineandcyclohexanone.The
formationoftheenamineisreversible,however,throughhydrolysis(Trakanrungroj,2015).This
enaminewillactasthenucleophile.Themechanismfortheenamineisshownbelow.

Figure1:Mechanismofenamine

Waterisaproductinthisreaction.Thetolueneandwaterareanazeotropebecausethey
evaporateandcondensetogetherintheHickmanhead.Whenthisazeotropeisremovedfromthe
reaction,itpushesthereactiontowardstheproductsside.ThisisbecauseofLeChateliers
Principle.Thisistheprinciplethatthereactionwantstobeatequilibrium.Therefore,whenthere
isachangeintemperature,concentration,volumeandpressure,thereisashifteithertowardsthe
reactantsortheproducts.Distillationusesheattoseparatecompounds.Distillationallowsa
changeinequilibrium.TheHickmanheadremovestheazeotropeandthenreactionmoves

towardstheproductsinordertocounteractthechange.Themechanismofalphaacylationof
enamineandtheapparatusfordistillationareshownbelow.

Figure2:DistillationApparatus

Figure3:Mechanismofalphaacylationofenamine


Oncetheenamineiscreated,itreactswithaceticanhydridetoformtheacylated
salt(Trakanrungroj,2015).Inweek2,thereactionmixtureishydrolyzedandthenpurified.
Hydrolizationoccursthroughreflux.Refluxallowsheattobeaddedtothereactionwhilenot
losinganyreactants.Themechanismforhydrolysisandtheapparatusforrefluxareshown
below.

Figure4:Mechanismofhydrolysis


Figure5:HydrolysisApparatus

Next,extractionisusedtoseparatetheaqueouslayerandorganiclayer.Purificationisexecuted
throughcolumnchromatography.Columnchromatographyisusedtoseparatesample
compounds(
Jandera&Churck,1985
).Thisprocessoccursbecauseofadifferencein
polarity.Themorepolaracompoundis,thesloweritwillmovethroughthepolaralumina.This
allowsfortheseparationincompounds.Theapparatusforcolumnchromatographyisshown
below.


Figure6:ColumnChromatographyApparatus

Finally,Infraredspectrum(IR)isusedtoidentifytheproductmade.Thisisdonebydetermining
thebondsinacertaincompound.Functionalgroupscanthenbeidentifiedbasedonthebonds
present.

Procedure
:

Topreparetheenamine,thereactiontookplacein10mLroundbottomflask.The
reactants,cyclohexanone,toluene,ptoluenesulfonicacidmonohydrate,andpyrrolidine,wereall
addedtotheroundbottomflaskandattachedtodistillationapparatus,asshowninfig.2.The
reactionwasdistilledfor30minutesat140.Distillatewasremovedfromdistillheadinorder
tomovethereactiontowardstheproducts.Toprepare2acetylcyclohexanone,anacetic
anhydrideandtoluenemixturewasthenaddedtothereaction.

Afterthemixturehadsatuntilnextlab,waterwasaddedandthehydrolysisapparatus
wassetup,asshowninfig.5.Themixturewasthenboiledandstirredfor30minutesat120.
Morewaterwasthenaddedandthebottomlayerextractedanddiscarded.hydrochloricacidwas
added,thebottomlayerextractedandthendiscarded.Theorganiclayerwasdriedwithgranular
anhydroussodiumsulfate.Next,thetoluenewasevaporatedina70waterbath.Thenthe
organiclayerwaspurifiedthroughcolumnchromatographyinaPasteurpipetasthecolumn,
aluminaastheabsorbentandmethylenechlorideastheeluent.Aftercolumnchromatography,
themethylenechloridewasevaporatedinawarmwaterbathat50.TheweightandIRwas
thentaken.

Data
:

Compound

cyclohexane

toluene

ptoluenesulfonicacid

pyrrolidine

Starting
Amount

0.06g

4.0mL

20mg

0.54mL

Table1:Beginningamountsofreactants

Compound

Theoretical
Yield(g)

Experimental
Yield(g)

PercentYield

2acetylcyclohexanone

0.086g

0.26g

303%

Table2:Productyields


Figure7:IRofFinalProduct

Compound

Bond/FunctionalGroup

2acetylcyclohexanone sp3C H

KnownWavelength
29952850 cm1

sp2C sp2O

1715 cm1

sp2C sp2C

16501600 cm1

Table3:IRbondspresentin2acetylcyclohexanone

Calculations
:

TheoreticalYield:

1molcyclohexanone
0.06gcyclohexanone 98.1gcyclohexanone
1mol2acetylcyclohexanone
140.2g2acetylcyclohexanone
1molcyclohexanone
1mol2acetylcyclohexanone = 0.0857g

PercentYield:

actualyield
0.26g2acetylcyclohexanone
theoreticalyield 100 = 0.0857g2acetylcyclohexanone 100 = 303%

Discussion/Conclusion
:

Infraredspectroscopywasusedtoidentifythefinalproduct.ThebondspresentintheIR
are sp2C H , sp3C H ,and sp2C sp2O .The sp2C H wasidentifiedassuchbecausethe
peakwasat3067.2 cm1 .Thisbondiswithinthe31003000 cm1 range.Thepeakat2926.38
cm1 wasidentifiedas sp3C H bondsbecauseitiswithinthe29952850 cm1 range.The
sp2C sp2O bondwasidentifiedassuchbecauseitspeakat1672.00 cm1 isneartherangeof
1715 cm1 .Thereforetheproductmaybethestartingreactant,cyclohexanone.Theproduct
cannotbethedesiredproduct,2acetylcyclohexanonebecauseitdoesnothavebondsforanOH
oranaromatic.TheIRfor2acetylcyclohexaneshouldhaveshown sp3C H bondsat
29952850 cm1 , sp2C sp2O bondsat1715 cm1 ,and sp2C sp2C at16501600 cm1 .
SincetheIRdoesnotmatchtheknownIRof2acetylcyclohexanone,itcannotbethedesired
product.Insteaditismorelikelytobecyclohexane.
Somesourcesoferrormayhavebeennotallowingthecreationoftheenamineorthe
productatthetimesofreaction.Bothsynthesisesneededheatandtimetoreact.Insufficientheat
andtimecouldhavepreventedthesereactionstooccurfullyoratall.Anothererroristhatthe
organiclayermayhavebeenevaporatedwhenheatwasapplied.Itwasnotedthatduring
distillation,thebrownliquidevaporatedquicklyafterthe30minuteinterval.Someofthe
productcouldhaveevaporated.
Thepercentyieldwas303%.Thisisahugeerrorbecausethetoluenewasprobablynot
evaporatedalltheway,leavingtheendweighttobesignificantlyhigherthanthetheoretical
yield.TheIRdidnotshowthatthecorrectproductwasproduced.Thiscouldalsoaffecttheend
weight,explainingthepercentyield.


Citations
:

1.Pavia,D.
OrganicChemistryLabManualCHM238
CengageLearning:Mason,OH,2011

2.
P.Jandera,J.Churck,(1985),
GradientElutioninColumnLiquidChromatography:Theory
andPractice
,JournalofChromatographyLibrary,31.3495.
https://books.google.com/books?hl=en&lr=&id=0WfYjrb2VgsC&oi=fnd&pg=PP2&dq=column
+chromatography+definition&ots
=90FPc3GhwG&sig=xz_SJl8r3g9kZFT321LsKmNyU4#v=on
epage&q=column%20chromatography%20definition&f=false

3.Trakanrungroj,Pichaya,
EnamineReactions
,Recitationslides,2015.
https://myasucourses.asu.edu/bbcswebdav/pid10987662dtcontentrid48380695_1/courses/201
5SpringTTrakanrungroj/Week_1_Enamine_Presentation%282%29.pdf

4.Trakanrungroj,Pichaya,
EnamineReactions:Week2
,Recitationslides,2015.
https://myasucourses.asu.edu/bbcswebdav/pid11010785dtcontentrid48732241_1/courses/201
5SpringTTrakanrungroj/Week_2_Enamine_Presentation%282%29.pdf