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Chemistry

Получение коранулен-функционализированного Hexahelicene по меди (I) -catalyzed алкине-азида циклоприсоединения непланарной полиароматических единиц

Published: September 18th, 2016

DOI:

10.3791/53954

1GIR MIOMeT, IU CINQUIMA, Área de Química Inorgánica, Universidad de Valladolid

Здесь мы приводим протокол для синтеза сложного органического соединения, состоящего из трех неплоских полиароматических единиц, легко монтируется с разумным выходом.

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.

Благодаря своей особой геометрии, коранулен и гелицены представляют собой молекулы , которые могут принять структуру далеко от плоскостности и рождают интересные свойства. В 1-15 За последние несколько лет, поиск молекулярных рецепторов для углеродных нанотрубок и фуллеренов является очень активной областью 16-19 в связи, главным образом, их потенциального применения в качестве материалов для органических солнечных батарей, транзисторов, датчиков и других устройств. 20-28 отличная взаимодополняемость в форме между коранулен и фуллерена привлекли внимание нескольких исследователей с целью проектирования молекулярные рецепторы , способн....

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1. Функционализация 2,15-Dimethylhexahelicene

  1. Dibromination из 2,15-dimethylhexahelicene
    1. Взвесить 0,356 г (1,0 ммоль) 2,15-dimethylhexahelicene, 0,374 г (2,1 ммоль) свеже перекристаллизовывают N -bromosuccinimide (NBS) и 24 мг (0,07 ммоль) перекиси бензоила (ВРО) (70% мас с 30% вода в качестве стабилизатора). Поместите все т.......

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Коранулен (3 а) и 2,15-dimethylhexahelicene (3 б) могут быть получены в соответствии текущими методами 46-48 в простой моды с очень хорошими выходами (рисунок 5). Оба имеют общую молекулу, 2,7-диметилнафталин, в качестве исходного матери.......

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Окончательное соединение 7 было подготовлено после того, как 6 шагов от неплоских полиароматических предшественников 3 и 3b с умеренной до очень хорошими выходами при каждой реакции. Основное ограничение наблюдалось в этом маршруте была бромировани?.......

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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.

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NameCompanyCatalog NumberComments
2,15-DimethylhexaheliceneN/AN/APrepared according to reference 5b,c in the main text.
CorannuleneN/AN/APrepared according to reference 5a in the main text.
N-Bromosuccinimide (NBS)Sigma AldrichB8.125-5ReagentPlus®, 99%. Recrystallized from hot water.
Benzoyl peroxide (BPO)Sigma AldrichB-2030~70% (titration). 30% water as stabilizer.
Sodium azideSigma AldrichS2002ReagentPlus®, ≥99.5%.
Gold (III) chloride HydrateSigma Aldrich50778puriss. p.a., ACS reagent, ≥49% Au basis.
EthynyltrimethylsilaneSigma Aldrich21817098%.
[PdCl2(dppf)]N/AN/APrepared according to reference 6 in the main text.
CuIN/AN/APrepared according to reference 7 in the main text.
KFSigma Aldrich30759999%, spray-dried.
(+)-Sodium L-ascorbateFluka11140BioXtra, ≥99.0% (NT).
Copper(II) Sulphate 5-hydratePanreac131270for analysis.
Carbon tetrachloride (CCl4)Fluka87030for IR spectroscopy, ≥99.9%.
Dichloromethane (DCM)Fisher ScientificD/1852/25Analytical reagent grade. Distilled prior to use.
HexaneFisher ScientificH/0355/25Analytical reagent grade. Distilled prior to use.
Ethyl acetateScharlauAC0145025SReagent grade. Distilled prior to use.
Tetrahydrofuran (THF)Fisher ScientificT/0701/25Analytical reagent grade. Distilled prior to use.
1,2-Dichloroethane (DCE)Sigma AldrichD6,156-3ReagentPlus®, 99%.
Methanol (MeOH)VWR20847.36AnalaR NORMAPUR.
Triethyl amine (NEt3)Sigma AldrichT0886≥99%.
Silica gelAcros360050010Particle size 40-60mm.
Sand - low ironFisher ScientificS/0360/63General purpose grade.
TLC Silica gel 60 F254Merck1.05554.0001
Monowave 300 (Microwave reactor)Anton Para
SonicatorGrupo Selecta30005136 Litres.

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