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Summary
Abstract
Introduction
Protocol
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Chimica

Framställning av en Corannulene-funktionaliserad Hexahelicene av koppar (I) -catalyzed alkyn-azid cykloaddition av icke-plan Polyaromatiska Units

Published: September 18, 2016
doi:
10.3791/53954
, ,
1GIR MIOMeT, IU CINQUIMA, Área de Química Inorgánica,Universidad de Valladolid

Summary

Här presenterar vi ett protokoll för att syntetisera en komplex organisk förening som består av tre icke-plana polyaromatiska enheter monteras enkelt med rimliga utbyten.

Abstract

The main purpose of this video is to show 6 reaction steps of a convergent synthesis and prepare a complex molecule containing up to three nonplanar polyaromatic units, which are two corannulene moieties and a racemic hexahelicene linking them. The compound described in this work is a good host for fullerenes. Several common organic reactions, such as free-radical reactions, C-C coupling or click chemistry, are employed demonstrating the versatility of functionalization that this compound can accept. All of these reactions work for planar aromatic molecules. With subtle modifications, it is possible to achieve similar results for nonplanar polyaromatic compounds.

Introduction

På grund av sin speciella geometri, corannulene och helicenes är molekyler som kan anta en struktur långt ifrån planhet och ger upphov till intressanta egenskaper. 1-15 Under de senaste åren, är sökandet efter molekylära receptorer för kolnanorör och fullerener ett mycket aktivt område 16-19 beror huvudsakligen på deras potentiella tillämpningar som material för organiska solceller, transistorer, sensorer och andra enheter. 20-28 den utmärkta komplementaritet i form mellan corannulene och en fulleren har uppmärksammats av flera forskare i syfte att utforma molekylära receptorer som kan medföra supramolekylära föreningen genom spridningskrafter. 29-39

Kemin av de ovan nämnda icke-plana polyaromatiska föreningar liknar det som beskrivits för helt plana molekyler, men det är ibland svårt att hitta lämpliga förhållanden för att uppnå önskade selektiviteter och utbyten. 40 </sup> I detta arbete presenterar vi syntesen av en molekyl (7) har tre polyaromatiska enheter i några få steg med goda utbyten genom att tillämpa enkla och typiska tekniker som finns i varje forskningslaboratorium. Molekylen är av stor betydelse, eftersom det kan anta en tångliknande konformation att etablera goda interaktioner med C 60 37 i lösning; och det kan öppna en forskningslinje som en potentiell receptor för högre kirala fullerener tack vare helicene länk, som är en kiral molekyl på grund av förekomsten av ett stereo axel. 41-45 kommer dock endast racemiskt helicene användas i detta arbete.

Vid denna punkt, är den enda begränsningen att syntetisera dessa receptorer framställningen av helicenes och corannulenes, eftersom de inte är kommersiellt tillgängliga. Men, enligt nya metoder publicerats på annat håll 46-48 de kan erhållas i lämpliga mängder på ett rimligt kort tidsperiod.

Protocol

1. Funktionalisering av 2,15-Dimethylhexahelicene Dibromination av 2,15-dimethylhexahelicene Väg 0,356 g (1,0 mmol) 2,15-dimethylhexahelicene, 0,374 g (2,1 mmol) av nyligen omkristalliserad N-bromsuccinimid (NBS) och 24 mg (0,07 mmol) av bensoylperoxid (BPO) (70% vikt med 30% av vatten som stabilisator). Placera alla fasta ämnen i en 100 ml Schlenk-kolv med en magnetisk omrörarstav. Sätts under kväveatmosfär genom tre cykler av gas evakuering, följt…

Representative Results

Corannulene (3 a) och 2,15-dimethylhexahelicene (3 b) kunde framställas enligt gängse metoder 46-48 på ett rättframt sätt med mycket goda utbyten (Figur 5). Båda delar en gemensam molekyl, 2,7-dimetylnaftalen, som utgångsmaterial, vilket ger upphov till en divergerande till konvergent syntes av den slutliga molekylen. <im…

Discussion

Slutlig förening 7 har upprättats efter 6 steg från icke-plana polyaromatiska prekursorer 3 a och 3 b med måttlig till mycket goda utbyten vid varje reaktion. Den största begränsningen observerats i denna väg var brome både icke-plana polyaromatiska föreningar. Men i fallet med föreningen 4 en, en viktig mängd fri corannulene kan återvinnas för ytterligare användningar. Syntesen av <strong…

Divulgazioni

The authors have nothing to disclose.

Acknowledgements

This work was funded by the Spanish Ministerio de Economìa y Competitividad (CTQ 2013-41067-P). H.B. acknowledge with thanks a MEC-FPI grant.

Materials

2,15-Dimethylhexahelicene N/A N/A Prepared according to reference 5b,c in the main text.
Corannulene N/A N/A Prepared according to reference 5a in the main text.
N-Bromosuccinimide (NBS) Sigma Aldrich B8.125-5 ReagentPlus®, 99%. Recrystallized from hot water.
Benzoyl peroxide (BPO) Sigma Aldrich B-2030 ~70% (titration). 30% water as stabilizer.
Sodium azide Sigma Aldrich S2002 ReagentPlus®, ≥99.5%.
Gold (III) chloride Hydrate Sigma Aldrich 50778 puriss. p.a., ACS reagent, ≥49% Au basis.
Ethynyltrimethylsilane Sigma Aldrich 218170 98%.
[PdCl2(dppf)] N/A N/A Prepared according to reference 6 in the main text.
CuI N/A N/A Prepared according to reference 7 in the main text.
KF Sigma Aldrich 307599 99%, spray-dried.
(+)-Sodium L-ascorbate Fluka 11140 BioXtra, ≥99.0% (NT).
Copper(II) Sulphate 5-hydrate Panreac 131270 for analysis.
Carbon tetrachloride (CCl4) Fluka 87030 for IR spectroscopy, ≥99.9%.
Dichloromethane (DCM) Fisher Scientific D/1852/25 Analytical reagent grade. Distilled prior to use.
Hexane Fisher Scientific H/0355/25 Analytical reagent grade. Distilled prior to use.
Ethyl acetate Scharlau AC0145025S Reagent grade. Distilled prior to use.
Tetrahydrofuran (THF) Fisher Scientific T/0701/25 Analytical reagent grade. Distilled prior to use.
1,2-Dichloroethane (DCE) Sigma Aldrich D6,156-3 ReagentPlus®, 99%.
Methanol (MeOH) VWR 20847.36 AnalaR NORMAPUR.
Triethyl amine (NEt3) Sigma Aldrich T0886 ≥99%.
Silica gel Acros 360050010 Particle size 40-60mm.
Sand – low iron Fisher Scientific S/0360/63 General purpose grade.
TLC Silica gel 60 F254 Merck 1.05554.0001
Monowave 300 (Microwave reactor) Anton Para
Sonicator Grupo Selecta 3000513 6 Litres.
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Tags

Keywords: CorannuleneHexaheliceneCopper(I)-catalyzed Alkyne-azide CycloadditionNonplanar Polyaromatic UnitsClick ChemistryRadical ReactionsCarbon-carbon CouplingDebrominationColumn Chromatography
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Álvarez, C. M., Barbero, H., Ferrero, S. Preparation of a Corannulene-functionalized Hexahelicene by Copper(I)-catalyzed Alkyne-azide Cycloaddition of Nonplanar Polyaromatic Units. J. Vis. Exp. (115), e53954, doi:10.3791/53954 (2016).
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