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Chimica

Utarbeidelse av en Corannulene-funksjon Hexahelicene av kobber (I) -catalyzed alkyn-azid cykloaddisjon av plane Polyaromatiske Units

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

Summary

Her presenterer vi en protokoll for å syntetisere en kompleks organisk forbindelse som består av tre ikke-plane polyaromatiske enheter, sette sammen og med rimelige utbytter.

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 grunn av sin spesielle geometri, corannulene og helicenes er molekyler som kan vedta en struktur langt fra planhet og gir opphav til interessante egenskaper. 1-15 I de siste årene, er søk av molekylære reseptorer for karbon nanorør og fulle et svært aktivt område 16-19 på grunn av, i hovedsak, til deres potensielle anvendelser som materiale for organiske solceller, transistorer, sensorer og andre enheter. 20-28 den utmerkede komplementaritet i form mellom corannulene og en Rene har tiltrukket seg oppmerksomheten av flere forskere med sikte på å utforme molekylære reseptorer i stand til å etablere supra forening av sprednings krefter. 29-39

Kjemien av de ovenfor nevnte ikke-plane polyaromatiske forbindelser er lik den som er beskrevet for fullstendig plane molekyler, men det er noen ganger vanskelig å finne egnede betingelser for å oppnå de ønskede selektiviteter og utbytter. 40 </sup> I dette arbeidet vil vi presentere syntesen av et molekyl (7) som har tre polyaromatiske enheter i noen få skritt med godt utbytte ved å bruke enkle og typiske teknikker som finnes i alle forskningslaboratorium. Molekylet er av stor betydning fordi det kan innta en tangan konformasjon for å etablere gode interaksjoner med C 60 37 i oppløsning; og den kan åpne en forskningslinje som en potensiell reseptor for høyere kirale fuller takket være helicene linkeren, som er et chiralt molekyl på grunn av eksistensen av en stereogenisk akse. 41-45 vil imidlertid bare racemisk helicene brukes i dette arbeidet.

På dette punktet, er den eneste begrensning for å syntetisere disse reseptorene er fremstillingen av helicenes og corannulenes, ettersom de ikke er kommersielt tilgjengelige. Men, i henhold til nye metoder i andre sammenhenger 46-48 kan de oppnås i egnede mengder på en rimelig kort tid.

Protocol

1. funksjonalisering av 2,15-Dimethylhexahelicene Dibromination av 2,15-dimethylhexahelicene Veie 0,356 g (1,0 mmol) 2,15-dimethylhexahelicene, 0,374 g (2,1 mmol) friskt omkrystallisert N-bromsuccinimid (NBS) og 24 mg (0,07 mmol) benzoylperoksyd (BPO) (70% vekt med 30% av vann som stabilisator). Legg alle faste stoffer i en 100 ml Schlenk-kolbe med en magnetisk rørestav. Satt under nitrogenatmosfære ved hjelp av tre sykluser med gass evakuering etterfulg…

Representative Results

Corannulene (3 a) og 2,15-dimethylhexahelicene (3-b) kan fremstilles etter dagens metoder 46-48 på en enkel måte med meget gode utbytter (figur 5). Begge deler en felles molekyl, 2,7-Dimethylnaphthalene, som utgangsmateriale, noe som gir opphav til en divergerende til konvergent syntese av det endelige molekylet. <img alt="Fig…

Discussion

Endelig forbindelsen 7 er utarbeidet etter 6 trinn fra ikke-plane polyaromatiske forløpere 3 a og 3 b med moderat til svært god avkastning på hver reaksjon. Den største begrensningen observert i denne ruten var bromeringen av både ikke-plane polyaromatiske forbindelser. Imidlertid, i tilfelle av forbindelse 4 en, en viktig mengde av fri corannulene kan gjenvinnes for videre bruk. Syntesen av <stron…

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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