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Chimica

إعداد Hexahelicene functionalized Corannulene من قبل النحاس (I) -catalyzed Cycloaddition آلكاين-أزيد من وحدات Nonplanar العطرية المتعددة

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

Summary

هنا، نقدم بروتوكول لتجميع مركب عضوي معقد يتكون من ثلاث وحدات العطرية المتعددة nonplanar، وتجميعها بسهولة مع عوائد معقولة.

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

نظرا لاحتياجاتهم الخاصة الهندسة، corannulene وhelicenes هي عبارة عن جزيئات يمكن أن تبني الهيكل بعيدا عن بلاناريتي وتؤدي إلى خصائص مثيرة للاهتمام. 1-15 وفي السنوات القليلة الماضية، والبحث من المستقبلات الجزيئية لأنابيب الكربون النانوية والفلورين هي منطقة نشطة للغاية 16-19 بسبب، بشكل رئيسي، إلى التطبيقات المحتملة كمواد للخلايا العضوية الشمسية، والترانزستورات، وأجهزة الاستشعار وغيرها من الأجهزة. 20-28 وقد اجتذبت التكامل الممتاز في الشكل بين corannulene والفوليرين انتباه العديد من الباحثين بهدف تصميم مستقبلات جزيئية قادرة على تشكيل جمعية supramolecular من قبل قوات التشتت. 29-39

كيمياء المركبات العطرية المتعددة nonplanar المذكورة أعلاه مماثلة لتلك التي وصفها لجزيئات مستو تماما، ولكن من الصعب أحيانا أن تجد الظروف المناسبة لتحقيق الإختياريات والعوائد المرجوة. 40 </sup> في هذا العمل نقدم تركيب جزيء (7) وجود ثلاث وحدات العطرية المتعددة في خطوات قليلة مع عوائد جيدة من خلال تطبيق تقنيات سهلة ونموذجية وجدت في كل مختبر أبحاث. جزيء له أهمية كبيرة لأنه يمكن أن تبني التشكل تشبه الكماشة لإقامة تفاعلات جيدة مع C 60 37 في الحل. وأنه قد فتح خط الأبحاث بمثابة مستقبلات المحتملة لارتفاع الفلورين بفضل مراوان إلى رابط helicene، وهو جزيء انطباقي بسبب وجود محور stereogenic. 41-45 ومع ذلك، لن يستخدم إلا في helicene الرزيمية في هذا العمل.

في هذه المرحلة، والقيد الوحيد لتجميع هذه المستقبلات هي إعداد helicenes وcorannulenes، لأنها ليست متاحة تجاريا. ولكن، وفقا لأساليب جديدة نشرت في أماكن أخرى 46-48 يمكن الحصول عليها بكميات مناسبة في فترة قصيرة معقولة من الزمن.

Protocol

1. Functionalization من 2،15-Dimethylhexahelicene Dibromination من 2،15-dimethylhexahelicene تزن 0.356 غرام (1.0 ملمول) من 2،15-dimethylhexahelicene، 0.374 غرام (2.1 ملمول) من بلورته حديثا -bromosuccinimide N (الم…

Representative Results

Corannulene (3 أ) و 2،15-dimethylhexahelicene (3 ب) يمكن إعداد التالية الأساليب الحالية 46-48 بطريقة واضحة مع غلة جيدة جدا (الشكل 5). نشترك جزيء المشترك، 2،7-dimethylnaphthalene، كمادة البدء، مما أدى إلى متباينة إلى التوليف متقارب?…

Discussion

وقد تم إعداد مجمع النهائي 7 بعد 6 خطوات من السلائف العطرية المتعددة nonplanar 3 أ و 3 ب مع معتدلة إلى غلة جيدة جدا في كل رد فعل. وكان القيد الرئيسي لوحظ في هذا الطريق والبرومين كل من المركبات العطرية المتعددة nonplanar. ومع ذلك، في حال…

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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