Name:MohitMulani ExperimentDueDate:11/20/13 Sectioninstructor:Dr.

ThomasKwokSection:223

DehydrobrominationofMesostilbeneDibromide,GC/MSAnalysis Abstract This experiment carries out the conversion of mesostilbene dibromide to 1,2 diphenylethyne via concerted E2 reactions. Vacuum filtration and recrystallization are then used to extract and purify the desired product which is put through the Bayer and Br2/Ch2Cl2 tests for unsaturation. It is also further analyzed through Gas Chromatography/Mass Spectrometry. MP is 5759C, GC times are 11.10 for 1,2 diphenylethyne and 12.07fortransitioncompound(1bromoethene1,2diyl)dibenzene.M/zvalues forproductare178.2and179.2fortransitioncompoundtheyare258.2and260.2, Introduction

(antiperiplanarconformation)

This compound is rotated 120 degrees so H andBrareantiperiplanarandE2reactioncanoccur.The transition state haloalkene is synperiplanar because it has a double bond which cannotberotated.This state is more stable than an anti transition state and therefore requires more energy for the second E2 mechanism. This is why we need a high temperature and the addition of triethylene glycol helps add energy for bond rotation and elimination by increasing the boiling point of the solution. In the first E2 mechanism, the Bromine attaches to the K+ from KOH and the hydrogen donates its electron tothe

single bond. InthesecondE2mechanism,thesamethinghappensbutthetwogroups(HandBrleaving group)areinsynperiplanarorientation.Thetemperatureatthesereactionsis190200C.

After the reaction, to separate out the desired 1,2 diphenylethyne from KBr, we add water and place the room temperature cooled solution in an ice bath. The KBr, being polar is soluble inwaterenabling us to perform vacuum filtration. This is done with a Hirsch funnel and a vacuum flask with a side tube that is attachedtorunningwatertocreateavacuum.Afterthecrudeproduct(insoluble)iscollected,we have to further purify it. To do this we recrystallize inverysmallamountsof95%ethanol.Thisinvolves the addition of ethanol to the crude mixture and heating in a hot water bath until most everything dissolves. Then the crude mixture is cooled inanicebathandvacuumfiltrationisperformed again.This final insoluble product is purified 1,2 diphenylethyne an assumption that is tested and confirmed by analysis. Gas chromatography and mass spectrometry are also used to analyse our product. The gas chromatography divides substances into 2 phases (a gaseous mobile phaseandliquidstationaryphase) which utilizes relative vapour pressure and polarity differences. The data collected from this is called

Retention time and is the time between when the compound is entered into the injection port and its elution.Amassspectrometerionizesthe compoundsandgivesusspectralpeaksonagraph,abundance vs (m/z). The parent molecular ion which is formed by the ionization is usually at the highestm/zpoint and its abundance can be seen on the graph. Isotopes in several cases can be accounted for in these graphs by minor (or major depending on the proportion of isotopes to each other) peaks around the mainion.

SECTION2:RESULTS
Reagents/Products Equivalents MW (g/mol) /Density (g/cm3) 1 340.05g/mol Moles Theoretical wt/volume Actual Mass orVolume (Purified,g) 0.3037g

0.00089

0.3037g

259.15g/mol

0.0012

0.3037g

0.035

178.24g/mol

0.00003 1 0.00346

0.3037g

0.0055g

KOH

3.88 56.1056g/mol

0.1945g

0.1945g

mesostilbenedibromideisthelimitingreagent.

MPofproductisseentobe5759C.

OBSERVATIONS:
Action ObservedChange

Put the mixture of meso stilbene dibromide, Mixtureisbrownishcolour KOHandtriethyleneglycolonaheatingblock Onheatingat190200C. Add4mlwaterandputinicebath Addethanolandheatfilteredoutppt Coolinicebath Mixture starts boiling vigorously and solid precipitates Someofthemixturedissolves,substantialamount ofprecipitateremainsundissolved Mostpptdissolves,someremains Whitecrystalsbeginforming

Add 5mg product to tube and add 1 drop After the first drop, the solution turns colourless. bromine in dichloromethane. Add some more After the second and third drops, a pale colour drops forms. Add to 5mgproductand2ml95%ethanoldrops One drop causes change in colour to purple in of KMnO4 and compareobservation todrops of both cases, however the purple colour change in KMnO4addedtocontrolofethanol. the control (ethanol) is much deeper than the purplecolouroftheproductethanolmix.

SpectroscopicData(GC/MSanalysis)
GCPeakRetention DetectedMass(M/Z) Time(minutes) Structure

11.08

179.2
with113C

11.08

178.2
withno13C

12.10

260.2
with81Br

12.10

258.2
with79Br

12.10

180.3
with113C

12.10

179.3
withno13C

Calculations: Moles=GivenMass/MolMass =0.3037g/340.05g/mol =0.00089moles

SECTION3
Methods/Procedures The procedure is takenfromGilbert,J.C.,Martin,S.F.,ExperimentalOrganicChemistry,AMiniscale and Microscale Approach, 403405, 93101, 867868. There were no significant deviations from the assignedprocedure.

Discussionandinterpretationofresults The experiment ran how we expected it to. The desired product 1,2 diphenylethyne is clearly formed alongwithsomeofthetransitionhaloalkene(1bromoethene1,2diyl)dibenzene. This much can be concluded from the GC/MS data. Two retention times are seen on the GC graph, 11.10 and 12.07. From the MS graph (they work complementary to each other) we can tell that the 11.10representstheproductand12.07representsthetransitioncompound.Therelativeabundancesof thesetellusthatmoreofthetransitioncompoundwaspresentinthesamplethatwasinjected. From the MS data, we see theproduct inthe firstgraphat11.10minutes.Ithasthem/zvalueof178.2 and 179.2 representing the M and M+1 peak we can expect when the isotopes 12C and 13C are present. The percentage probability of the M+1 peak is about 15% the natural proportion is 99:1but as there are 14 carbons in this product,theprobabilityandsizeofpeakisincreased.At12.07minutes, we see the transition compound at 258.2 and 260.2. The difference in these peaks is caused by the presence of 81Br and 79Br. The proportion of these is almost equal and soarethesizes ofthepeaks.As the exact ratio is about 0.51:0.49, we see a little higher peak for 79Br.Wealsoseepeaksat180.3and 179.3. These represent the transition compound withthebromineremoved(hencethepositive charge). Thedifferentisotopesofcarbonareagainrepresented.

Examining the GC/MS data, we come to the conclusion that as the mechanism predicted, we have formed 1,2 diphenylethyne ny E2 reaction. Comparing with the chemical tests, we can conclude that none of the original meso compound was left (as the tests checked for unsaturation and the original compound was saturated). The chemical tests couldnt have distinguished between the transition compound and the final product as they werebothunsaturated.ThiswheretheGC/MSdatawasmore specific. The GC data by itself too wouldnt be a reliable way to identify compounds, but when used together, the GC/MS graphs tell us the final compounds we have created. Thus the GC separates out the coumpounds andtheMSgivesusspecificdata aboutthemassofthecompoundssowecanidentify them. By themselves, the individual methods face limitations that can be overcome by using them together. Even then however, it is prone toerrors.Includingthechanceoffalse positivesandnegatives, any mistakes made while performing separation with Gas chromatography carry over to the Mass Spectrometerinfluencingthespectraweget(creatingnoiseonthegraph). Errors in this graph are manifested in the form of the transition compound still being present with the product. This implies that the whole reaction didnt occur which means the energy wasnt enough to favour the entire second E2 mechanism. As is seen from GC/MS analysis and the MP (5759C),the product isnt completely pure 1,2 diphenylethyne. The presence of imurities could be external or from thetransitioncompound(1bromoethene1,2diyl)dibenzene.

Conclusions: At the end of the experiment, we have used GC/MS analysis to conclude the formationoftheproduct 1,2diphenylethyneandatransitionhaloalkene.TheBayertestandBromineindicholoromethanetesttell us that the product we have is unsaturated (i.e either an alkene or alkyne) which is what can be

confirmed through GC/MS. The meso compound wasnt completely converted into the product which explainsthelowyieldandGC/MSspectra.

References Gilbert, J. C., Martin, S. F., Experimental Organic Chemistry, A Miniscale andMicroscaleApproach, 5thedition