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窒素酸化物を用いてアジドフリーなメタロジアゾメタン合成

  • 0Faculty of Chemistry and Biochemistry, Ruhr-University Bochum, Universitaetsstrasse 150, Bochum 44801, Germany.
Journal of the American Chemical Society +

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2024年8月20日

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2024年8月20日

PubMedで要約を見る

まとめ

この要約は機械生成です。

研究者は,金属化イリドと窒素酸化物から安定したアルカリ金属ダイアゾメタニドを合成した. この安全な方法は,様々な化学合成のための多用途のダイアゾ化合物を提供します.

科学分野

  • 有機化学
  • 合成化学
  • 有機金属化学

背景

  • ダイアゾ化合物は重要な合成反応剤である.
  • 伝統的な合成方法には 危険な材料が含まれています
  • ダイアゾ化合物の製造にはより安全な代替品が必要である.

研究 の 目的

  • ダイアゾ化合物を合成するための 新しく安全な方法を開発する.
  • アルカリ金属ダイアゾメタニドを分離し,特徴づけること.
  • これらの新しい化合物の合成の応用を探求する.

主な方法

  • 金属化イリドと窒素酸化物 (N2O) の反応
  • [3 + 2]サイクロアディションを含むウィティグのようなメカニズム.
  • アルカリ金属ダイアゾメタニドの分離と特徴付け

主要な成果

  • アルカリ金属ダイアゾメタニドの合成と分離が成功しました
  • 金属化ダイアゾメタンの熱安定性の向上が示された.
  • 観測された特徴的な短いC-N距離と赤色シフトのN-N振動.
  • 移行金属複合体,1,2,3-トリアゾール,ダイアゾアセテート,アルキンの合成を含む多用途が示された.

結論

  • アルカリ金属ダイアゾメタニドは従来のダイアゾ化合物より安全で安定した代替品です.
  • この新しい合成経路は,様々な化学的変換のための貴重な中間物質へのアクセスを提供します.
  • この方法は,有機合成におけるダイアゾ化学の有用性を拡大する.

関連する概念動画

1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO<sub>2</sub> Mechanism 01:37

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Nitrous acid is a relatively weak and unstable acid prepared in situ by the reaction of sodium nitrite and cold, dilute hydrochloric acid. In an acidic solution, the nitrous acid undergoes protonation when it loses water to form a nitrosonium ion—an electrophile. Nitrous acid reacts with primary amines to give diazonium salts. The reaction is called diazotization of primary amines.

Figure 1. The mechanism of the diazotization reaction of primary amines.
As illustrated in Figure 1, in the...

Diazonium Group Substitution: –OH and –H 01:19

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Nitrous acid, a weak acid, is prepared in situ via the reaction of sodium nitrite with a strong acid under cold conditions. This nitrous acid prepared in situ reacts with primary arylamines to form arenediazonium salts. Such reactions are known as diazotization reactions. As shown in Figure 1, the formation of arenediazonium salts begins with the decomposition of nitrous acid in an acidic solution to give nitrosonium ions.

Figure 1.
A primary arylamine attacks the nitrosonium ion to form an...

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Arenediazonium substitution reactions occur when the diazonium group is substituted by various functional groups such as halides, hydroxyl, nitrile, etc. For instance, arenediazonium salts react with copper(I) salts of chloride, bromide, or cyanide to form corresponding aryl chlorides, bromides, and nitriles. These reactions are named Sandmeyer reactions. Although the mechanism of this reaction is complicated, as illustrated in Figure 1, they are believed to progress via an aryl copper...

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Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...

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Carboxylic acids react with diazomethane in an ether solvent via alkylation at the carboxylate oxygen atom to give methyl esters of the corresponding acid with excellent yields.

Diazomethane is a yellow gas having a boiling point of −23 °C. It is conveniently prepared by the action of a base on N-methyl-N-nitrosourea or N-methyl-N-nitrosotoluenesulphonamide.
The esterification mechanism involves the protonation of diazomethane by the carboxylic acid to yield a carboxylate salt and...

Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic S<sub>N</sub>1 01:14

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Treating arylamines with nitrous acid gives aryldiazonium salts that are effective substrates in nucleophilic aromatic substitution reactions. The diazonio group in these salts can be easily displaced by different nucleophiles, yielding a wide variety of substituted benzenes. The leaving group departs as nitrogen gas, and this easy elimination is the driving force for the substitution reaction.
In the Sandmeyer reaction, for example, the diazonio group is replaced by a chloro, bromo,...