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Improved Reaction Conditions for Rhodium-Catalyzed Hydroarylation

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Improved Reaction Conditions for Rhodium-Catalyzed Hydroarylation Improved Reaction Conditions for Rhodium-catalyzed Hydroarylation of C60 Fullerenes with Tolylboronic acid Towards bis[60] fullerene dumbbells Master thesis in Chemistry, 30 HP By Gustav Hulu Supervisors: Helena Grennberg and Michael Nordlund Subject specialist: Lukasz Pilarski Examiner: Christer Elvingson Department of Chemistry - BMC June 19, 2018 Abstract Reaction optimization was performed for a rhodium-catalyzed hydroary- lation of fullerenes with para-tolylboronic acid, where [Rh(cod)(MeCN)2]BF4 was used as a catalyst. The starting 3:1 mixture of ortho-dichlorobenzene and water was based on previous research. In our hands it gave a yield of 34%. By optimization of the solvent system, a yield of 71% was obtained in a 7:1 mixture of ortho-dichlorobenzene and tert-butanol. Furthermore, for the reaction to function efficiently, it was found that water is essential. Quan- titative 1H NMR spectroscopy was used, with dimethyl terephthalate as an internal standard, to calculate the yield. i Sammanfattning En reaktionsoptimering utf¨ordesf¨oren rodiumkatalyserad hydroarylering av fullerener med para-tolylborsyra, d¨ar[Rh(cod)(MeCN)2]BF4 anv¨andessom katalysator. Startbetingelserna var en 3:1-blandning av orto-diklorbensen och vatten som baserades p˚atidigare forskning. Med eget arbete gav detta ett utbyte p˚a34%. Genom optimering av l¨osningsmedelssystemet s˚akunde ett utbyte p˚a71% uppn˚as. Detta med en 7:1-blandning orto-diklorbensen och tertbutanol. For att reaktionen ska fungera effektivt s˚auppt¨acktes det att vatten var n¨odv¨andigt. Kvantitativ 1H NMR-spektroskopi anv¨andes,med dimetyltereftalat som intern standard, f¨oratt best¨ammautbytet. ii Popul¨arvetenskaplig sammanfattning p˚asvenska Hela universum best˚arav atomer, av olika sorters grund¨amnen. Ett av de vanli- gaste ¨arkol, vilket ¨armed och bygger upp allt levande. Om ett grund¨amnekan finnas i flera former s˚akallas dessa former f¨orallotroper. De mest k¨anda¨ardia- mant och grafit (den senare finns i bland annat blyertspennor). Diamant har en speciell kristallstruktur och grafit best˚arav lager p˚alager av kol, d¨arlagren best˚ar av hexagoner. En ny allotrop av kol som kallades f¨orfulleren uppt¨acktes 1985. Fulleren ¨aren sf¨ariskform av kol, som en boll uppbyggd av kolatomer. Uppt¨ackarna av fullerener fick Nobelpriset i kemi 1996, d˚adetta var en viktig uppt¨ackt. Den vanli- gaste fullerenen inneh˚aller60 kolatomer, C60, och har en form som kallas f¨orstympad ikosaeder. Denna kan ses i figur 1. Den best˚arav 20 hexagoner och 12 pentagoner och har 60 h¨orn,d¨arvarje h¨orn¨aren kolatom. Denna form ¨arv¨alk¨and,d˚adet ¨ardet m¨onstersom fotbollar brukar ha, med svarta pentagoner och vita hexagoner. C60 och C70 ¨arde fullerener som ¨arvanligast och mest anv¨anda. Efter dess uppt¨ackt Figur 1: En tredimensionell figur av C60 blev fullerener ett hett och sp¨annandeforsknings¨amne.Mycket forskning lades ner p˚adess egenskaper, till¨ampningaroch reaktivitet. Modifierade man fulleren kunde den f˚aegenskaper som kunde anv¨andasinom bland annat elektronik, medicin och solceller. Men bakom dessa modifikationer l˚agdet m˚anga˚arsgrundforskning p˚ahur fullerener kan reagera. Att forska p˚amolekylers reaktivitet ¨arviktigt. Det kan ¨oppna m˚angad¨orrarf¨oratt kunna skapa helt nya molekyler. De flesta reaktioner som har visat sig fungera p˚afullerener ¨arinte helt nya, utan har kunnat baseras p˚atidigare reaktioner. Det ¨arreaktioner som har fungerat p˚amolekyler med liknande egen- skaper som fullerener. Fullerener ¨arelektronegativa och tar g¨arnaupp elektroner. I deras struktur kan man likna dem som alkener, kolf¨oreningarmed dubbelbind- ningar. D¨arf¨orborde fullereners reaktivitet likna den f¨orelektronfattiga alkener. Man har kunnat visa att m˚angav¨aletableradereaktioner f¨orelektronfattiga alkener fungerar f¨orfullerener. En av dessa ¨ar rodiumkatalyserad hydroarylering med aryl- borsyror. Rodium ¨aren metall, och kan vara en del av en katalysator. Katalysatorer iii Figur 2: Exempel p˚a molekyler i detta projekt: para-tolylborsyra, orto- diklorbensen, tert-butanol och produkten. ¨arett begrepp f¨orf¨oreningarsom g¨oren reaktion snabbare, t.ex. de avgasrenande katalysatorerna som finns i bilar snabbar p˚areaktionen att bilda ofarliga gaser av skadliga. Hydroarylering betyder att man l¨agger till ett v¨ateoch en arylgrupp till en dubbel- eller trippelbindning. Aryler best˚arav aromatiska f¨oreningar,t.ex. bensen. Arylborsyror ¨arborsyror med en arylgrupp p˚akopplad. Denna reaktion har ut- forskats v¨aloch blivit etablerad f¨orelektronfattiga alkener. D¨arf¨orkom en japansk forskargrupp p˚aatt testa denna sorts reaktion med fullerener, och det fungerade. De lyckades hitta en bra katalysator. Men sj¨alva utbytet (hur mycket produkt som skapas) var inte s¨arskilth¨ogt(40%). Anledningen till varf¨ordenna sorts reaktion ¨arintressant ¨aratt den kan utvecklas f¨oratt skapa s.k. fullerenhantlar. En fullerenhantel ¨artv˚afullerener sammankop- plade med ett molekylsegment, d¨arberoende p˚avad molekylsegmentet ¨ar,kan ha intressanta egenskaper. Dessa har fr¨amsthaft till¨ampningarinom solceller, men m˚alet¨aratt g˚afr˚anhantlar till l˚angakedjor av fullerener. Dessa kan liknas vid p¨arlhalsband,d¨ar sn¨oret¨armolekylsegmenten och p¨arlornafullerener. Anv¨and- ningen f¨ordessa ¨arelektriska ledningar p˚amolekylniv˚a. N¨arvi g˚armot mindre elektriska apparatarer har f¨altetmolekyl¨arelektronik vuxit fram, d¨arman f¨ors¨oker bygga elektroniska komponenter p˚amolekylniv˚a.Att skapa dessa l˚angakedjor ¨ar v¨aldigtkomplicerat, vilket ¨aranledningen varf¨orm˚angab¨orjarmed att skapa hant- lar. Tidigare arbete vid Organisk kemi i Uppsala har b¨orjatmed att l¨arasig om hur reaktionen fungerat, samt att b¨orjabygga molekylsegmenten. Molekylsegmenten ¨ar diborsyror, d¨arman kopplar en fulleren p˚avarje sida. Eftersom molekylsegmenten tar l˚angtid att tillverka, s˚avill man att reaktionen ska fungera s˚abra som m¨ojligt innan man anv¨anderdem. H¨arb¨orjarmitt arbete, att optimera rodiumkatalyserad hydroarylering av fullerener med arylborsyror. I dessa experiment anv¨ands para- tolylborsyra, en enkel och l¨attillg¨angligborsyra. F¨oratt optimera denna reaktion s˚a¨ardet viktigt att unders¨oka vilket l¨osningsmedel, vilken reaktionstid och vilken temperatur som fungerar b¨ast.F¨orstupprepades tidi- iv gare experiment f¨oratt f˚aett grepp om hur reaktionen fungerade. Efter detta var n¨astasteg att utveckla l¨osningsmedelsystemet. N¨artv˚aolika v¨atskor inte kan blanda sig med varandra och bildar tv˚aolika faser kallas det f¨ortv˚afassystem.Ett exempel p˚atv˚afassystem ¨ari salladsdressingar, d¨arvin¨agernoch oljan bildar tv˚aolika lager d˚ade inte kan blandas. I denna reaktion anv¨ands orto-diklorbensen (ett organiskt l¨osningsmedel,f¨orkortas o-DCB) och vatten. De kan inte blandas med varandra och eftersom fulleren ¨arv¨aldigtsv˚arl¨osligts˚akr¨avso-DCB. Eftersom vatten p˚ast˚as kr¨avas i ett av stegen i reaktionen, och fulleren kan endast l¨osasi den organiska fasen, s˚asker reaktionen endast d¨arvatten och o-DCB m¨ots.Om det fanns m¨ojlighetatt utf¨orareaktionen i ett enfassystem, d¨arallting kan blandas, s˚akunde reaktionen f¨orb¨attras. D¨arf¨ortestades reaktionerna med alkoholer ist¨alletf¨orvatten. Alko- holer kan l¨osasi o-DCB men har ¨aven vattenliknande egenskaper, s˚avi hoppades att de skulle fungera. De anv¨andaalkoholerna var etanol, isopropanol och tert- butanol. Eftersom de ¨armer opol¨ara¨anvatten s˚akan de blandas med o-DCB. Som f¨orv¨antat gav alkoholerna b¨attreresultat ¨anvatten, reaktionen med tert-butanol gav n¨astandubbelt s˚abra utbyte som tidigare resultat (71% mot 40%). Detta var ett genombrott v¨aldigttidigt, och kunde dessutom reproduceras i flera experiment. Ex- perimenten fortsatte med variationer i reaktionstid, d¨ar3 timmar visade sig ge bra resultat i oljebad. Sedan b¨orjadetemperaturerna varieras, men under den h¨ardelen av projektet b¨orjadereaktionerna ge annorlund resultat ¨anf¨orut. Utbytena sj¨onk j¨amf¨ortmed tidigare resultat och en fels¨okningsprocess b¨orjade.Utrustningen och kemikalierna unders¨oktesnoggrant, med m˚angatestexperiment och analyser. Efter ett l˚angtarbete s˚ahittades felk¨allan,vattenhalten i den anv¨andaalkoholen. Tert- butanol ¨arunik bland alkoholerna med att den ¨arfast vid rumstemperatur (den sm¨altervid ca. 25◦C). Men finns vatten i den, fr˚anungef¨ar1%, s˚a¨arden flytande vid rumstemperatur. I b¨orjanav studien anv¨andes"det flytande” i k¨arlet,men efter m˚angaexperiment var alkoholen mer fast. Det var d˚autbytena sj¨onk.Skapade vi en blandning av tert-butanol med 0.5% tillsatt vatten s˚akunde tidigare resultat uppn˚as. En promille vatten g¨oratt det finns n¨astanlika m˚angavattenmolekyler som fullerenmolekyler. D¨arf¨orr¨acker n˚agrapromille vatten f¨oratt det ska finnas tillr¨ackligt mycket. Detta ¨ari linje med tidigare forskningsresultat, inklusive en spansk molekylsimuleringsstudie, som visar att vatten ¨arett krav f¨oratt reaktionen ska ske, men inte entydligt att det ¨arjust vatten som kr¨avs. Sammanfattningsvis s˚ahar vi hittat ett effektivt enfassystem d¨aralla komponenter ¨arl¨ostamed tillr¨ackligt mycket vatten f¨oratt reaktionen ska ske. F¨or mycket vatten f¨ors¨amrarf¨orm˚aganf¨orfulleren att l¨osasig och reagera. Den stora f¨orb¨attringenav reaktionens effektivitet ger goda m¨ojligheter till ¨okad anv¨andning. v Acknowledgements I would like to thank Helena and Michael for being great supervisors on this very interesting project. I would also like to thank the rest of the members of the AGHG laboratory for making this semester a blast. vi Abbreviations and symbols o-DCB ortho-dichlorobenzene cod 1,5-cyclooctadiene DCTB 2-[(2E)-3-(4-tert-Butylphenyl)-2-methylprop-2-enylidene]malononitrile DMT Dimethyl terephtalate Et Ethyl EWG Electron-withdrawing group IPR Isolated pentagon rule iPr Isopropyl MALDI Matrix-assisted laser desorption/ionisation Me Methyl MiW Microwave MS Mass Spectrometry NMR Nuclear Magnetic Resonance NOESY Nuclear Overhauser effect spectroscopy tBu Tertiary butyl vii Contents Popul¨arvetenskaplig sammanfattning p˚asvenska iii 1 Introduction 1 1.1 Carbon allotropes . 1 1.2 Fullerene, its properties and applications .
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