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Chemistry

銅（I）によるコランニュレン官能Hexaheliceneの調製は、非平面多環芳香族ユニットのアルキンアジド付加環を - 触媒

Published: September 18th, 2016

DOI:

10.3791/53954

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

ここでは、合理的な収率で容易に組み立てる3非平面多環芳香族単位から構成される複雑な有機化合物を合成するためのプロトコルを提示します。

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.

それらの特別な幾何学、コランニュレンとヘリセンが遠い平面から構造を採用し、興味深い特性を生じさせることができる分子であるに。ここ数年では1月15日 、カーボンナノチューブやフラーレンのための分子の受容体の探索は非常に活発な地域であります有機太陽電池、トランジスタ、センサーやその他のデバイス用材料としての可能性アプリケーションに、主に起因16-19。20-28コランニュレンとフラーレンとの間の形状に優れた相補性は設計の目的で、いくつかの研究者の注目を集めています分散力によって超分子会合を確立することができる分子の受容体。29-39

上記非平面の多環芳香族化合物の化学的性質は完全に平面分子について記載したものと同様であるが、所望の選択性および収率を達成するための適切な条件を見出すことが困難な場合がある。40 、（7）すべての研究室で見つかった、簡単で一般的な技術を適用することにより、良好な収率でいくつかの手順で3多環芳香族単位を有する分子の合成を提示します。それは溶液中でC 60 37との良好な相互作用を確立するために、ペンチのような構造をとることができるので、分子が非常に重要です。それが原因での立体軸が存在するキラル分子であるヘリセンリンカーに高いキラルフラーレンの....

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1.機能化 2,15-Dimethylhexahelicene

  1. 2,15-dimethylhexaheliceneの二臭素
    1. の30％と（過酸化ベンゾイル（BPO）の2,15-dimethylhexaheliceneの0.356グラム（1.0ミリモル）に、新たに再結晶のNブロモスクシンイミド（NBS）の0.374グラム（2.1ミリモル）および24mgの（0.07ミリモル）を計量し、70％の重量安定剤としての水）。磁気攪拌棒を備えた100ミリリットルシュレンクフラ?.......

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コランニュレン（3 a）と2,15-dimethylhexahelicene（ 図3b） は、非常に良好な収率（ 図5）との直接的なやり方で現在の方法46-48以下調製することができます。両方の最終的な分子の収束合成の発散を生じる、出発物質として、一般的な分子、2,7-ジメチルナフタレンを共有します。

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最終化合物7は、非平面の多環芳香族前駆体からの6つのステップ3aと各反応における中等度から非常に良好な収率で3 bの後用意されています。このルートで観察された主な制限は、両方の非平面多環芳香族化合物の臭素化しました。しかしながら、化合物4の場合には、遊離コランニュレンの重要な量は、さらに使用?.......

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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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