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Abstract
Introduction
Protocol
Results
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Chemistry

Udarbejdelse af en Corannulene-funktionaliserede Hexahelicene af Kobber (I) -catalyzed Alkyn-azid Cycloaddition af ikke-plane Polyaromatiske Units

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

Summary

Her præsenterer vi en protokol til at syntetisere en kompleks organisk forbindelse består af tre ikke-plane polyaromatiske enheder, samles let med rimelige udbytter.

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 af deres særlige geometri, corannulene og helicenes er molekyler, der kan vedtage en struktur langt fra planhed og giver anledning til interessante egenskaber. 1-15 I de sidste par år, søgning af molekylære receptorer for kulstof nanorør og fullerener er et meget aktivt område 16-19 skyldes hovedsageligt, at deres potentielle anvendelser som materialer til organiske solceller, transistorer, sensorer og andre enheder. 20-28 den fremragende komplementaritet i form mellem corannulene og en fulleren har tiltrukket sig opmærksomhed fra flere forskere med det formål at designe molekylære receptorer kan godtgøre supramolekylære association ved dispersion kræfter. 29-39

Kemien af de ovennævnte ikke-plane polyaromatiske forbindelser svarer til den, der er beskrevet for fuldstændigt plane molekyler, men det kan være vanskeligt at finde egnede betingelser for at opnå de ønskede selektiviteter og udbytter. 40 </sup> I dette arbejde præsenterer vi syntesen af et molekyle (7), der har tre polyaromatiske enheder i et par skridt med gode udbytter ved at anvende let og typiske teknikker findes i alle forskningslaboratorium. Molekylet er af stor betydning, fordi det kan indtage en pincer-lignende konformation til at skabe gode interaktioner med C 60 37 i opløsning; og det kan åbne en forskning linje som en potentiel receptor for højere chirale Fullerener takket være helicene linker, som er et chiralt molekyle på grund af eksistensen af et stereogent akse. 41-45 vil dog kun racemisk helicene anvendes i dette arbejde.

På dette tidspunkt, den eneste begrænsning for at syntetisere disse receptorer er fremstillingen af ​​helicenes og corannulenes, da de ikke er kommercielt tilgængelige. Men ifølge nye metoder offentliggjort andetsteds 46-48 de kan fås i passende mængder i en rimelig kort periode.

Protocol

1. Funktionalisering af 2,15-Dimethylhexahelicene Dibromination af 2,15-dimethylhexahelicene Afvej 0,356 g (1,0 mmol) 2,15-dimethylhexahelicene, 0,374 g (2,1 mmol) frisk omkrystalliseret N-bromsuccinimid (NBS) og 24 mg (0,07 mmol) benzoylperoxid (BPO) (70 vægt-% med 30% af vand som stabilisator). Anbring alle faste stoffer i en 100 ml Schlenk-kolbe med en magnetisk omrører. Sat under nitrogenatmosfære ved tre cykler af gas evakuering efterfulgt af genp?…

Representative Results

Corannulene (3 a) og 2,15-dimethylhexahelicene (3 b) kunne fremstilles ved at følge de nuværende metoder 46-48 på en enkel måde med meget gode udbytter (figur 5). Begge deler en fælles molekyle, 2,7-dimethylnaphthalen, som udgangsmateriale, hvilket giver anledning til en divergent til konvergent syntese af den endelige molekyle. <p class="jove_content" fo:keep-together.within-page="al…

Discussion

Final forbindelse 7 er udarbejdet efter 6 trin fra ikke-plane polyaromatiske forstadier 3 a og 3 b med moderat til meget gode udbytter på hver reaktion. Den største begrænsning observeret i denne rute var bromeringen af ​​både ikke-plane polyaromatiske forbindelser. Men i tilfælde af forbindelse 4 a, en vigtig mængde frit corannulene kan genvindes til yderligere anvendelsesformål. Syntesen af…

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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