JoVE Journal > Chemistry
Summary
Abstract
Introduction
Protocol
Results
Discussion
Disclosures
Acknowledgements
Materials
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Chemistry

Preparazione di un Hexahelicene corannulene-funzionalizzati da rame (I) -catalyzed Acetilene-azide cicloaddizione di unità non planare policiclici aromatici

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

Summary

Qui, vi presentiamo un protocollo per sintetizzare un complesso composto organico composto da tre unità poliaromatici non planari, montato facilmente con rendimenti ragionevoli.

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

Grazie alla loro particolare geometria, corannulene e helicenes sono molecole che possono adottare una struttura lontano dalla planarità e dar luogo a proprietà interessanti. 1-15 Negli ultimi anni, la ricerca dei recettori molecolari per nanotubi di carbonio e fullereni è una zona molto attiva 16-19 a causa, principalmente, alle loro potenziali applicazioni come materiali per le celle organiche solari, transistor, sensori e altri dispositivi. 20-28 l'ottima complementarietà di forma tra il corannulene e un fullerene hanno attirato l'attenzione di numerosi ricercatori, con l'obiettivo di progettare recettori molecolari in grado di stabilire un'associazione supramolecolare da parte delle forze di dispersione. 29-39

La chimica dei composti poliaromatici non planari suddetti è simile a quella descritta per le molecole totalmente planari, ma a volte è difficile trovare condizioni adatte per raggiungere le selettività e le rese desiderati. 40 </sup> In questo lavoro presentiamo la sintesi di una molecola (7) avente tre unità poliaromatici in pochi passi con buone rese applicando tecniche semplici e tipiche presenti in ogni laboratorio di ricerca. La molecola è di grande importanza perché può adottare una conformazione tenaglia per stabilire buone interazioni con C 60 37 in soluzione; e può aprire una linea di ricerca come potenziale recettore per maggiori fullereni chirali grazie al linker eliceni, che è una molecola chirale a causa dell'esistenza di un asse stereogenico. 41-45 Tuttavia, solo eliceni racemico saranno utilizzati in questo lavoro.

A questo punto, l'unica limitazione per sintetizzare questi recettori è la preparazione di helicenes e corannulenes, dal momento che non sono disponibili in commercio. Ma, secondo i nuovi metodi pubblicati altrove 46-48 possono essere ottenuti in quantità adatte in un breve periodo di tempo ragionevole.

Protocol

1. Funzionalizzazione di 2,15-Dimethylhexahelicene Dibromination di 2,15-dimethylhexahelicene Pesare 0,356 g (1,0 mmol) di 2,15-dimethylhexahelicene, 0,374 g (2,1 mmoli) di -bromosuccinimide appena ricristallizzato N (NBS) e 24 mg (0,07 mmoli) di perossido di benzoile (BPO) (70% in peso con il 30% di acqua come stabilizzatore). Mettere tutti i solidi in un pallone da 100 ml Schlenk con ancoretta magnetica. Mettere in atmosfera di azoto da tre cicli di evac…

Representative Results

Corannulene (3 a) e 2,15-dimethylhexahelicene (3 b) può essere preparato secondo i metodi attuali 46-48 in modo semplice con ottime rese (Figura 5). Entrambi condividono una molecola comune, 2,7-dimetilnaftalene, come materiale di partenza, dando luogo a una divergente alla sintesi convergente della molecola finale. <img alt="F…

Discussion

Composto finale 7 è stato preparato dopo 6 passi da precursori poliaromatici non planari 3 A e 3 B da moderata a molto buone rese in ogni reazione. La limitazione principale osservata in questo percorso è stata la bromurazione di composti poliaromatici non planari. Tuttavia, nel caso del composto 4 bis, una quantità importante di corannulene libero può essere recuperato per altri usi. La sintesi di …

Disclosures

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

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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