CHEM2122008

Experiment4
ProcedureforWeeks1&2

HowCanaComplex
AlkenebeSynthesized?

R Br

R Mg Br

R' O

A.HowcanaGrignardReactionbeSuccessfullyAccomplished?
PrelabAssignment:
1. Read:
ThisExperimenthandout
2. InYourNotebook:
a. Prepare a Table of Compounds including the names, mol. wts., bps, densities and
solubilitiesinwaterandorganicsolventsforbromobutane,2methylpropanal,2methyl
3heptanol,diethyletherandmagnesiummetal(nameandmolwt.only).
b. WritetheWasteDisposalInstructions.
Category3: Bromobutane.
Category4: 2Methylpropanal.
Category5: Conc.H2SO4.
Category6: Allaqueousextracts.
Category7: Mg,sodiumsulfate.
Special:
Excessetherandetherdistillate>RecoveredEthercontainerinthehood.
Theforerunofthefractionaldistillation>Forerunwastecontainer.
c. Using complete structural formulas of ALL organic compounds used in this
experiment (Rs are not acceptable as symbols in the structures), write balanced
equationsfor:
Thepreparationofbutylmagnesiumbromide.
Thereactionofbutylmagnesiumbromidewith
o 2methylpropanal(Note:Thisisanaldehyde)
o water
o molecularoxygen
o carbondioxide
o unreacted1bromobutaneinthedryethersolution.
Thereactionsofaqueoussulfuricacidwith:
o themajororganicproduct
o thesideproductsfromthepreviousbullet.
d. Starting on a new set of facing pages, write a complete stepwise procedure for the
synthesisof2methyl3heptanolthroughSTEP4.#7.

CHEM212Experiment4

AlkeneSynthesis

e. PrepareamatchingResultssectionincludingyourcalculatedvaluesforthevolumeof
1bromobutaneand2methylpropanal,aswellas,thegramsofmagnesiumneededforthe
synthesis.Includeallofyourcalculations.
3. On separate sheets of paper complete the flow diagram for the preparation and
purificationof2methyl3heptanol.Apartialflowdiagramframeworkisattachedattheend
ofthisactivity.Completionofthediagramrequiresfillinginblanksandadditionofboxes
forsomeofthefinalpurificationsteps.Placeyourflowdiagraminyourdatabinderunder
theExperiment4tab.

AlkeneSynthesis

CHEM212Experiment4

Introduction:
ForthissynthesiswehaveselectedoneofthefourGrignardreactionsthatresultedfromour
analysis.Thus,oursynthesiswillbeginwith1bromobutaneand2methylpropanal.
ThepreparationoftheGrignardreagent,RMgX,isrepresentedinequation(1),whereRX
dryether
(1)
RX+Mg
RMgX
solvent
represents1bromobutane.TheexactnatureoftheGrignardreagentinsolutionisnotknown.It
isbelievedtobeamixtureofnumerousspecies.Thesespeciesarehighlysolvatedbyetherand
are complexed with one another. It is customary to represent the Grignard reagent by the
formulaRMgXwhenwritingchemicalequations,butitshouldbekeptinmindthatthespecies
insolutionareofamuchmorecomplexnature.
Theethersolventisanessential partoftheGrignardreagent,foretherisknowntoforma
complexwiththemagnesiumthatispresentinthereagent. Severalcasesareknownwhere
Grignard reagents have been prepared in the absence of ether, but the yields are not good.
Satisfactoryyieldsareusuallyobtainedwhenetherispresent.Themostcommonethersolventis
diethylether,(C2H5)2O,duetoitslowcostandeaseofremoval(itsboilingpointis36C).The
organichalidemay,ingeneral,beofanyorganicsubstituent(alkyloraryl)andthehalidemay
bebromide,chloride,oriodide.
ThepreparationoftheGrignardreagentmustbecarriedoutunderanhydrousconditionsand,if
possible, intheabsence ofoxygen. Itisexceedingly important tomaintain completely dry
conditions throughout, for the presence of water inhibits the initiation of the reaction and
destroysthereagentonceitisformed.
TheacidbasereactionthatoccurswhentheGrignardreagentcomesincontactwithwateris
showninequation(2).
(2)
RMgX+H2O
RH+HOMgX
TheGrignardreagentisastrongbase,sinceoneofthecarbonatomsbearssubstantialnegative
charge(RMg++X).Asabase,theGrignardreagentremovesaprotonfromwater.Theoverall
effectisthehydrolysisofthereagent,withtheformationofahydrocarbon(RH)andabasic
magnesium salt which coats the unreacted magnesium and inhibits further formation of the
Grignardreagent.Thusitiscriticaltoexcludewaterfromthereactionmixture.Otherweakly
acidiccompoundssuchasalcoholsandcarboxylicacidsalsodestroytheGrignardreagentand
inhibitthereactionbyanalogousacidbasereactions.
In addition to the reaction with water, there are other side reactions that may occur during
formationoftheGrignardreagent,asshowninequations(35).
ReactionwithOxygen:
(3)
ROMgX
ROOMgX
RMgX+O
2

ReactionwithCarbonDioxide:
RMgX+ O

O
O

Couplingwiththeorganichalide:
RMgX+RX

MgX

RR+MgX2

(4)

(5)

Itispossibletominimizethesereactionsbytakingcertainprecautionswhencarryingoutthe
experimentalwork.Thereactionswithoxygenandcarbondioxidemaybeavoidedbycarrying

CHEM212Experiment4

AlkeneSynthesis

outthereactionunderaninertatmosphere(suchasnitrogenorheliumgas).Also,whendiethyl
etherisusedasasolvent,aninertgasisnotessentialsinceethersveryhighvaporpressure
excludesacertainamountofairfromthereactionvessel.
Thecouplingreaction[equation(5)]isanexampleofaWurtzreaction. Itisnotpossibleto
eliminatethiscouplingreactioncompletely,butitmaybeminimizedbyusingdilutesolutionsto
avoidlocalizedhighconcentrationsofhalide.Thisisdonebyusingveryefficientstirringandby
slowlyaddingthehalidetothemagnesiuminether. Normallytherateofadditionofhalide
(dissolvedinether)andtherateofreflux(whendiethyletherisused)shouldbeadjustedsothat
theyareaboutequal. Alkyliodidesaremuchmorepronetocouplingreactionsthanarethe
bromidesandchlorides,sothatthelatterarepreferableforpreparingGrignardreagentseven
thoughtheyarelessreactive. Ifwaterhasbeencarefullyexcluded,themostimportantside
reactionisthecouplingprocess,butitisnotasignificantproblem.OncetheGrignardreagentis
prepared,itisuseddirectlyinsubsequentreactions.Thesmallamountofbyproductsneednot
beseparatedfromthereagentbeforeaddingthecarbonylcompound.
Inoursynthesis,butylmagnesiumbromideispreparedfrom1bromobutane.Itisthenallowedto
reactwith2methylpropanaltogivethesaltof2methyl3heptanolasshowninequation(6),
andthesaltisprotonatedwithdilutesulfuricacid,equation(7).

CH
H
CH
CH
C
C
H
C
H
H
3CH
3
2
2
2
3
CH
CH
C
CH
CH
(6)
3CH
2CH
2CH
2MgBr+
3 O CH
3 OMgB
ROMgBr+H2O+ H2SO4

Mg+2+HSO4+Br+H2O

(7)

Theadditionof2methylpropanaltothesolutionofbutylmagnesiumbromideisdoneslowly
withstirring and,if necessary,cooling, since thereaction is highly exothermic and ether is
volatile. Thereaction iscompleted byaddingdiluteaqueoussulfuricacidtohydrolyzethe
magnesiumsaltandformthefinalorganicproduct.Inaddition,theaciddissolvestheinsoluble
basicmagnesiumsaltthatisformed.Withouttheacid,anunworkableemulsionmayresult.
Aftertheethersolutionoforganicproductshasbeenseparatedfromtheaqueoussolutionof
magnesium salts, it is extracted successively with solutions of sodium bisulfite, sodium
bicarbonateandsodiumchloridetoremovesomeunreactedstartingmaterial,someproductsof
the side reactions and excess water, respectively, from the ether. (You should be able to
determinethespecificreactionsinvolvedineachextraction.)Afterfurtherdrying,theetheris
removedandtheproductispurifiedbyfractionaldistillation.
ExperimentalProcedureWeeks1&2.
Synthesis.
STEP1: Calculationofreagentvolumesandmasses:
0.21moleof1bromobutane(measurebyvolume)
0.20moleofMg.(measurebymass)
0.21moleof2methylpropanal(measurebyvolume)
STEP2: PreparationoftheGrignardReagent:
1. Obtainthefollowingequipmentrequiredforthisstepbutdonotassembleituntilafter2.
A250mLroundbottomflask
AClaisenadapter
A125mLseparatoryfunnel
Arefluxcondenser

AlkeneSynthesis

CHEM212Experiment4

TwodryingtubesfilledwithCaCl2.
Amagneticstirringbar.
Twoblueplasticclips
BECERTAINTHATALLOFTHEGLASSWAREISSCRUPULOUSLYDRY!!
2. Toeliminateanypossiblefilmofmoistureinthereactionflask,addtherequiredamountof
magnesiumturningsandamagneticstirringbartotheroundbottomflaskandattacha
dryingtubetotheneck. Thenheattheflaskthoroughlybyplacingitinaheatingwell
(regulatorseton5)androtatingitfrequentlyuntiltheentireglasssurfaceishottothetouch.
Cooltheflasktoroomtemperaturebeforeproceeding.Astheflaskcools,itdrawsindryair
throughthecalciumchloridedryingtube.NOTE:Coolingcanbehastenedbyholdingthe
flaskunderastreamoftapwater.However,takecarethatnowaterenterstheflask.
3. SetuptheflaskwithaClaisenadaptercontainingarefluxcondenseronthestraightneckand
the separatoryfunnel onthe bentneck (seethe demonstration apparatus). Leavespace
undertheflaskforyourmagneticstirrer,aheatingwellorandicebath,ifneeded.
4. Pour10mLofanhydrousetherslowlydownthecondenserintothereactionflask.
5. Thencombinethe1bromobutanewith~30mLofanhydrousether,mixwellandpourthe
solutionintotheseparatoryfunnelandconnectadryingtubetothetopofthefunnel.
6. Obtainanadditional20mLofanhydrousetherandkeepitreadytoaddwhenthe
reactionbegins.(See8.below)
Read the following overview of the reaction initiation process. Use this overview to add
cautionstothereactionstepsratherthancopyingtheoverviewdirectlyintoyourprocedure.
Overview: Thereactionisinitiatedbymixingasmallportionofthealkylhalidesolution
with the magnesium metal. This is usually the most difficult part of the
procedure.Onceinitiated,thereactionisstronglyexothermic,sothesolution
mustbeimmediatelydilutedwiththeextra20mLofanhydrousethertoslow
thereaction downandtolimitthepossibilities ofsidereactions. Whenthe
initial burstofreaction begins tosubside,additionalalkylhalidesolution is
addedslowlytomaintainacontrolledrateofreaction[Asmonitoredbythe
boilingrateoftheethersolution].
7. Initiationofthereaction:Turnonthemagneticstirrerandadmitaportion(~5mL)ofthe
1bromobutanesolutionintotheflask. Evidencethatthereactionhasstartedwillbethe
appearanceofcloudinessandbubbling.Itmaytakeupto5min.forthereactiontostart.
Ifstirringisnotsufficienttoinitiatethereaction,asecondattempt,asdescribedhere,should
bemade. Disconnecttheflaskandholdingitinthepalmofonehand,crushapieceof
magnesium against the bottom withthe flattened endofalong stirringrod. Watch for
bubblesindicatinglocalboilingatthatspot.Youmayalsofeelthewarmthofreactionon
yourhand.Ifthereactionstillfails,reassembletheapparatus,andheattheflasktoboiling
withyourheatingwellandboilthesolutionfor~5min.Ifheatingalsofailstoinitiatethe
reaction,askyourinstructorforhelp.
8. Assoonasthereactionstarts, slowly pourtheadditional20mLofANHYDROUSether
(Seestep 6. above) downthecondenser todilutethereactionmixtureandthuslimitthe
possibilityoftheunwantedcouplingreaction.

CHEM212Experiment4

AlkeneSynthesis

9. Whentheinitialreactionburstsubsides,graduallyaddtheremainingcontentsofthefunnel
byallowingthesolutiontodripintothereactionflaskatarateof~1droppersec.(addition
shouldtakeabout15minutes)Ifthecondenserfloodsbadlywithether,cooltheflaskinan
icewaterbathforafewsecondsonlyandcontinue.
Note: Whenacondenserfloods,vaporrisesintoitfasterthanthecondensingliquidcan
flowdown.Theresultisescapeofvapor,sometimesnoticeableasturbidityintheairabove
thecondenser,andthefillingoftheinnermostsectionofthecondenserwith roilingor
turbulentliquid.
10. Whentheaddition iscomplete andthereaction begins tosubside,heatthemixture to
continueactiveboilinguntilpracticallyalloftheMghasdissolved(~20min.more)or
untiltheamountofunreactedMgdoesnotdecreasein5min.
STEP3: Preparationof2Methyl3heptanol
1. WhiletheGrignardsolutionisrefluxing(step 10. above),measureintotwodifferentdry
containersandcovertokeepdry:
0.21moleof2methylpropanal(measurebyvolume)
25mLanhydrousether
2. Whentheformationofthebutylmagnesiumbromideiscomplete,removetheheatingmantle
fromthesystemandcooltheflasktoroomtemperaturewithanicebath.
3. When thereaction flaskis at roomtemperature, combine the 2methylpropanal withthe
25mLofanhydrousether,mixwellandpourthissolutionintotheseparatoryfunnelthat
heldthe1bromobutanesolutioninSTEP2.
4. Turnonyourmagneticstirrerandbeginslowadditionofthe2methylpropanalsolutionto
thebutylmagnesiumbromidesolution.Bepreparedtocooltheflaskwithanicebathifthe
additionleadstouncontrolledrefluxing.Theadditionmayrequireasmuchas30min.After
theadditioniscomplete,allowthereactionmixturetostirforanadditional10min.
5. Placeabout150mLofcrushediceintoa500mLbeakerandadd9mLofconcentrated
sulfuricacid.Inahood,pourthereactionmixtureslowlyandwithstirringintotheiceacid
mixture. Continue stirring the mixture until all remaining magnesium has reacted and
dissolved.Aftertheadditioniscomplete,transferthecoldmixture,whichmaycontainsome
precipitate,toaseparatoryfunnelandshakeitgently.Theprecipitateshoulddissolve.
6. SeparatethelayerstransferringtheetherlayertoanErlenmeyerflask.
7. Extracttheaqueouslayerwithtwo25mLportionsofetherandaddtheseetherextractsto
theoriginaletherlayer.
8. RinsetheClaisenheadandreactionflaskwith6MHCl.AllowtheflasktositwiththeHCl
untilallremainingmagnesiumhasreactedanddissolved.ThenrinsetheClaisenheadand
reactionflaskwithwaterandacetone. Do NOT rinsethecondenserorseparatoryfunnel.
Returnallglasswaretotheappropriatebins.
9. Theproceduremaybestoppedatthispointifnecessary.Ifso,transferthecombinedether
layerstoanErlenmeyerflaskandstopperittightlywithacork.
STEP4: PreliminaryPurification
1. Extract thecombined ethersolutions (intheseparatory funnel)with30mLofsaturated
sodiumbisulfitesolutionventingthefunneltorelievepressure.

AlkeneSynthesis

CHEM212Experiment4

2. Extracttheetherlayerwithtwo30mLportionsof10%sodiumbicarbonatesolution,again
ventingthefunnelfrequently.
3. Test the pH of the aqueous phase after the second sodium bicarbonate extraction. The
solution should be as basic as the original sodium bicarbonate solution used for the
extraction.
4. Ifthe secondextract is not basicenough, extract the ether solution with another 30mL
portionofsodiumbicarbonateandcontinuetheseextractionsuntiltheaqueousphasetests
appropriatelybasicaftertheextraction.
5. Extracttheethersolutionwith30mLofsaturatedsodiumchloridesolution.
6. Removetheremainderofthewaterbydryingtheethersolutionoveranhydroussodium
sulfate.
7. Ifnecessary,stoppertheflasksnuglywithacork,markthesolventlevelandallowthe
solutiontostandoverthedryingagentuntilthenextlabperiod.
STEP5: FinalPurification.
1. Filterthesolutionfromthedryingagentthroughaflutedfilterintoa250mLroundbottom
flask(Ifthevolumeofthesolutionhasdecreasedsignificantly,youmayneedtoaddsome
ethersothatthefiltrationcanbeaccomplished).
2. Removemostoftheetherfromtheproductbysimpledistillation(remembertheboiling
chip).
3. When the vapor temperature rises about 20 C above the bp of ether, stop the simple
distillation. Thevolumeofsolutionleftinthepotshouldbeabout25mL.Thedistillate,
recoveredether,shouldbeplacedinthebottlesmarkedforit.
4. Transferthecontentsofthesimpledistillationpottoa50mLroundbottomflask,rinsethe
original flask with 3 mL of your simple distillation distillate (Recovered Ether), and
convertyoursimpledistillationapparatustoafractionalonebyaddingacolumnpackedwith
glassbeads.
5. Besurethatthethermometerbulbisproperlyadjustedinthestillhead.Insulatetheflaskand
stillheadwithglasswoolandAlfoil,andcontinuedistilling.
6. Collect any forerun boiling more than 3C below the products bp. separately from the
product, recordtheboilingrangeandapproximatevolumeoftheforerun thencollecta
productfractionwithaboilingrangeof~5Corless.
7. Record the boiling range and approximate volume of the product. If your yield of
2methyl3heptanolislessthan8mL,checkwithyourinstructor.Yourthermometermay
beincorrectlyplaced.
8. Weightheproductandcalculatethe%yield.
9. PlacetheproductinalabeledvialorflaskandkeepittightlystopperedfortheWeek3&4
procedure.Discardtheforeruninforerunwastecontainer.
PartialFlowDiagramFrameworkforthe
SynthesisandPurificationof2Methyl3Heptanol
Abbreviations
MHOH = 2methyl3heptanol
E = ether
Bu = C4H9
2mp = 2methylpropanal
= missingentry
Thisdiagramassumesthatatraceofwaterispresentintheoriginalreaction.

CHEM212Experiment4

AlkeneSynthesis

E,BuBr,Mg,
O2(trace),H2O(trace)
reflux

GasPhase
BuH

E,Mg,BuBr,BuOMgBr,Bu
First
Reaction Bu,BuCO2MgBr,
Solution O2(trace))
Add2mp
Second
Reaction
Solution
GasPhase
H2,BuH

Ether

E,Mg,BuBr,2mp,
O2(trace)
1.H2O,H2SO4
2.Etherextraction
3.Combineextracts

Aqueous
H2O,E(trace)
H3O+,HSO4
Mg2+

E,BuBr,2mp,H2O,O2(trace)

NaHSO3extraction

Aqueous
H2O,E(trace)
Na+,HSO3

Ether
E,H2O,O2(trace)
Completetheflowdiagrambyaddingother"boxes"forextractionanddistillationsteps