JoVE - Journal of Visualized Experiments
JoVE Visualize
Contact Us
このページは機械翻訳されています。他のページは英語で表示される場合があります。 View in English

熱 [2+2]サイクル添加によるX形サイクロブタン結合テトラポルフィリン

  • 0Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering , Nagoya University , Nagoya 464-8603 , Japan.
Journal of the American Chemical Society +

|

2018年6月22日

|

2018年6月22日

PubMedで要約を見る

まとめ

この要約は機械生成です。

ニッケル媒介反応は,二重サイクル化とサイクル添加によって新しいX形テトラポルフィリンを生成した. 亜鉛複合体の前駆者は赤色化学発光を発するディケトディポルフィリンを生成した.

科学分野

  • 有機化学
  • 超分子化学
  • 材料科学

背景

  • ポルフィーリンは様々な用途を持つ重要なマクロサイクル化合物です.
  • 新しいポーフィリン構造の開発は 先進的な材料にとって不可欠です
  • タンデム反応は複雑な分子構造への 効率的な経路を提供します

研究 の 目的

  • 新型X型サイクロブタン結合テトラポルフィリンを合成する
  • エテノ溶融二酸化ホルモンの反応性を研究する.
  • ポルフィリン複合体の化学発光特性について調べる

主な方法

  • ニッケル触媒によるエチニレン結合型ジブロモディポルフィリンのダブルサイクリング.
  • 熱 [2+2] サイクル添加反応
  • 亜鉛 (II) ポルフィリン複合体の合成と特徴付け

主要な成果

  • 高度反応性のあるエテノ融合型ディポルフィリンが成功して合成された.
  • X形サイクロブータン結合テトラポルフィリンは [2+2] サイクロアディションによって形成された.
  • ディケトディポルフィリン系は環境条件下で赤色化学発光を示した.

結論

  • この研究は,複雑なテトラポルフィリン構造への新しい合成経路を示しています.
  • ディケトディポルフィーリンは,光を発する装置での応用の可能性を示しています.
  • タンデム・サイクライゼーションとサイクロアディションは,ポルフィリン化学における強力な戦略を提供します.

関連する概念動画

[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction 01:16

12.6K

The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.

From a molecular orbital perspective, the interacting lobes of the two π systems must be in phase to permit...

Cycloaddition Reactions: MO Requirements for Thermal Activation 01:16

4.6K

Thermal cycloadditions are reactions where the source of activation energy needed to initiate the reaction is provided in the form of heat. A typical example of a thermally-allowed cycloaddition is the Diels–Alder reaction, which is a [4 + 2] cycloaddition. In contrast, a [2 + 2] cycloaddition is thermally forbidden.

The reaction occurs between the highest occupied molecular orbital (HOMO) of one π component and the lowest unoccupied molecular orbital (LUMO) of the other. These are known as...

<em>meta</em>-Directing Deactivators: –NO<sub>2</sub>, –CN, –CHO, –&NoBreak;CO<sub>2</sub>R, –COR, –CO<sub>2</sub>H 01:13

6.7K

All meta-directing substituents are deactivating groups. These substituents withdraw electrons from the aromatic ring, making the ring less reactive toward electrophilic substitution. For example, the nitration of nitrobenzene is 100,000 times slower than that of benzene because of the deactivating effect of the nitro group. The first step in an electrophilic aromatic substitution is the addition of an electrophile to form a resonance-stabilized carbocation. The energy diagrams for...

2° Amines to <em>N</em>-Nitrosamines: Reaction with NaNO<sub>2</sub> 01:20

5.5K

Secondary amines react with nitrous acid to form N-nitrosamines, as depicted in Figure 1. Nitrous acid, a weak and unstable acid, is formed in situ from an aqueous solution of sodium nitrite and strong acids, such as hydrochloric acid or sulfuric acid, in cold conditions. In the presence of an acid, the nitrous acid gets protonated. The subsequent loss of water results in the formation of the electrophile known as nitrosonium ion.

Figure 1. The nitration reaction of secondary amines
The...

S<sub>N</sub>2 Reaction: Kinetics 02:14

10.3K

Kinetic Studies and Significance
In a chemical reaction, a relationship exists between the concentration of reactants and the rate at which the reaction proceeds. The study to measure this relationship is known as the kinetics of a chemical reaction. Kinetic studies are used to deduce the rate law of a chemical reaction, which provides information about the species involved during the transition state of the rate-determining step. Thus, kinetic studies help to derive the mechanism of a...

S<sub>N</sub>2 Reaction: Mechanism 02:27

17.5K

The kinetic studies of SN2 reactions suggest an essential feature of its mechanism: it is a single-step process without intermediates. Here, both the nucleophile and the substrate participate in the rate-determining step.
The presence of the more electronegative halogen in the substrate creates a polarized carbon-halide bond. The halide pulls the electron cloud generating an electrophilic center at the carbon atom. Thus, the carbon atom carries a partial positive charge while the halide has a...