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Chemistry

הכנת Hexahelicene Corannulene הפונקציונלית ידי נחושת (I) -catalyzed אלקין-יזיד cycloaddition יחידות Nonplanar Polyaromatic

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

Summary

כאן, אנו מציגים פרוטוקול לסנתז תרכובת אורגנית מורכבת מורכבת משלוש יחידות polyaromatic nonplanar, התאספה בקלות עם תשואות סבירות.

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

בשל הגיאומטריה, corannulene ו helicenes המיוחד שלהם, הם מולקולות אשר יכול לאמץ מבנה רחוק planarity להצמיח תכונות מעניינות. 1-15 בשנים האחרונות, החיפוש של קולטנים מולקולריים עבור ננו-צינוריות פחמן פולרנים הוא אזור פעיל מאוד 16-19 בשל, בעיקר, ליישומים הפוטנציאל שלהם כחומריים עבור תאים סולריים אורגניים, טרנזיסטורים, חיישנים והתקנים אחרים. 20-28 המשלה המעולה בכושר בין corannulene וכן פולרן משך את תשומת לבם של כמה חוקרים במטרה בעיצוב קולטנים מולקולריים מסוגלים הקמת עמותה מולקולרית ידי כוחות פיזור. 29-39

הכימיה של תרכובות polyaromatic nonplanar הנ"ל דומה לזה שתואר עבור מולקולות מישוריים לחלוטין, אבל זה לפעמים קשה למצוא תנאים מתאימים כדי להשיג selectivities רצוי ותשואות. 40 </sup> בעבודה זו אנו מציגים את הסינתזה של מולקולה (7) בעל שלוש יחידות polyaromatic בעוד כמה צעדים עם תשואות טובות על ידי יישום טכניקות קלות טיפוסיות המופיעות בכל מעבדת מחקר. המולקולה היא בעלת חשיבות רבה, כי זה יכול לאמץ קונפורמציה מלקחיים דמויים להקים אינטראקציות טובות עם C 60 37 בתמיסה; והוא עשוי לפתוח קו מחקר כמו קולטן פוטנציאל הודות פולרנים כיראליות גבוה כדי והמקשר helicene, שהינה מולקולה כיראליות בשל קיומו של ציר stereogenic. 41-45 עם זאת, רק helicene רצמית ישמש בעבודה זו.

בשלב זה, המגבלה היחידה לסנתז קולטנים אלה היא ההכנה helicenes ו corannulenes, שכן הם אינם זמינים מסחריים. אבל, על פי שיטות חדשות שפורסם במקומות אחר 46-48 הם ניתן להשיג בכמויות מתאימות בתוך פרק זמן קצר זמן סביר.

Protocol

1. Functionalization של 2,15-Dimethylhexahelicene Dibromination של 2,15-dimethylhexahelicene לשקול 0.356 גרם (1.0 מילימול) של 2,15-dimethylhexahelicene, 0.374 גרם (2.1 מילימול) של -bromosuccinimide N recrystallized טרי (NBS)…

Representative Results

Corannulene (3 א) ו- 2,15-dimethylhexahelicene (3 ב) יכול להיות מוכן בא שיטות קיימות 46-48 בצורה פשוטה עם תשואות טובות מאוד (איור 5). שניהם חולקים מולקולה נפוצה, 2,7-dimethylnaphthalene, כחומר המוצא, והוליד מתבדרים סינתזה מתכנסת של המ…

Discussion

מתחם סופי 7 הוכן לאחר 6 צעדים מקדימים polyaromatic nonplanar 3 א ו 3 ב עם עד בינוני תשואות טובות מאוד בכל תגובה. המגבלה העיקרית שנצפתה מסלול זה היה bromination של תרכובות שניהם polyaromatic nonplanar. עם זאת, במקרה של מתחם 4 א, ​​בסכו…

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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