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Chimica

구리 (I)에 의해 Corannulene 기능화 Hexahelicene의 제조 비평 아로마틱 유닛 알킨 지드의 고리 화를 촉매 반응

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

Summary

여기서는 적당한 수율로 용이하게 조립 세 비평 폴리 방향족 단위로 이루어진 복잡한 유기 화합물을 합성하는 프로토콜을 제시한다.

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

그들의 특별한 기하학, corannulene 및 helicenes 훨씬 평탄에서 구조를 채택하고 흥미로운 속성에 상승을 제공합니다. 지난 몇 년 동안 1-15 수 분자이다 인해, 탄소 나노 튜브와 풀러렌을위한 분자 수용체의 검색은 매우 활성 영역입니다 16-19 인해, 주로, 유기 태양 전지, 트랜지스터, 센서 및 기타 장치 재료로서의 응용 가능성에. 20-28 corannulene와 풀러렌과 모양이 뛰어난 보완이 설계의 목적으로 여러 연구자들의 주목을 받고있다 분산 힘에 의해 초분자 관계를 구축 할 수있는 분자 수용체. 29-39

상술 한 비평 아로마틱 화합물의 화학 완전히 평면 분자에 대해 기재 한 것과 유사하지만, 원하는 선택성 및 수율을 달성하기에 적합한 조건을 찾기 위해 때때로 어렵다. 40 </sup>이 작품에서 우리는 모든 연구 실험실에서 발견 간단하고 일반적인 기술을 적용하여 좋은 수율 몇 단계의 세 폴리 방향족 단위를 갖는 분자 (7)의 합성을 제시한다. 이 용액 C 60 37 좋은 상호 작용을 확립 협공 같은 형태를 채용 할 수 있기 때문에, 분자는 매우 중요하다; 그리고 인해 입체 축선의 존재 키랄 ​​분자이다 helicene 링커에 높은 키랄 풀러렌 덕분에 대한 잠재적 인 수용체로서 연구 선을 열 수있다. 41-45은 그러나, 라 세미 helicene 본 작업에 사용된다.

상용화하지 않기 때문에,이 시점에서, 이들 수용체를 합성 할 수있는 유일한 제한은 helicenes 및 corannulenes의 제조이다. 그러나, 새로운 방법에 따라 그들이 합리적인 단기간에 적합한 양으로 얻을 수있다 46-48 다른 출판.

Protocol

1. 기능화 2,15-Dimethylhexahelicene 2,15-dimethylhexahelicene의 Dibromination 30 %가 벤조일 퍼 옥사이드 (BPO) (70 % 0.356 g (1.0 밀리몰) 2,15-dimethylhexahelicene에, 0.374 g (2.1 밀리몰)을 새로이 재결정 N의 -bromosuccinimide의 (NBS) 및 24 mg의 (0.07 밀리몰) 중량 체중 안정 화제로서 물). 자기 교반 막대 한 100㎖의 슈렌 크 플라스크를 놓고 모든 고체. 쉬 렌크 라인에 불활성 가스를 재…

Representative Results

Corannulene (3)과 2,15-dimethylhexahelicene (3 B)는 아주 좋은 수율 (그림 5)와 간단한 방식으로 현재의 방법을 46-48에 따라 제조 될 수있다. 두 최종 분자의 수렴 합성 발산 상승을주는 원료로서 일반적인 분자, 2,7- 디메틸 나프탈렌을 공유한다. <img alt="그림 5" src…

Discussion

최종 화합물 7 비평 아로마틱 전구체에서 6 단계 3 각 반응에서 중등도 아주 좋은 수익률 3 B 후 작성되었습니다. 이 경로에서 관찰 된 주요 제한은 모두 비평 아로마틱 화합물의 브롬화이었다. 그러나, 화합물 4의 경우, 무료 corannulene 중요한 양은 상기 용도로 회수 할 수있다. 4 (b)의 ?…

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

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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