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

トランスニトリレーションによるアリルハリドおよびフェノール誘導体のニオケタライズされた還元性シアネーション

  • 0Davenport Research Laboratories, Department of Chemistry , University of Toronto , 80 St. George Street , Toronto , ON M5S 3H6 , Canada.
Journal of the American Chemical Society +

|

2019年11月12日

|

2019年11月12日

PubMedで要約を見る

まとめ

この要約は機械生成です。

この研究では,安全なシアン化反応剤を用いてベンゾニトリルを合成するための新しいニッケル触媒法が導入されています. このプロセスは,医学的に重要な化合物を効率的に生成し,塩酸ブロミドで基板の範囲を拡大します.

科学分野

  • 有機化学
  • カタリシス
  • 合成方法論

背景

  • ベンゾニトリルは 医学的化学における 重要な基幹です
  • ベンゾニトリル合成のための既存の方法は,しばしば有毒なシアン化物源または厳しい条件を伴う.

研究 の 目的

  • ベンゾニトリル合成のための新しい,安全で効率的なニッケル触媒方法を開発する.
  • ベンチ安定の電離性シアン化反応剤,2-メチル-2-フェニルマロニトリル (MPMN) を利用する.

主な方法

  • アリル (偽) ハリドとMPMNのニッケル触媒による還元結合
  • ナトリウムブロミド (NaBr) を添加物として使用することを含む反応条件の最適化.

主要な成果

  • 医学的に重要なベンゾニトリルの合成が成功し,
  • MPMNの安全で効果的な電化シアン化物源としての有用性が実証された.
  • アリル塩化物,トシラート,トリフラートを含む基板の範囲の拡大

結論

  • 開発されたNi-触媒化された方法は,ベンゾニトリルへの実用的な経路を提供します.
  • MPMNは従来のシアン化物反応剤より安全な代替品です.
  • NaBrは,酸化添加を促進することによって,反応性の低いアリル電ophilesを活性化するのに重要な役割を果たします.

関連する概念動画

Preparation of Nitriles 01:12

2.5K

One of the common methods to prepare nitriles is the dehydration of amides. This method requires strong dehydrating agents like phosphorous pentoxide or boiling acetic anhydride for converting amides to nitriles. Another reagent namely, thionyl chloride also accomplishes the dehydration of amides, where amide acts as a nucleophile. The first step of the mechanism involves the nucleophilic attack by the amide on the thionyl chloride to form an intermediate. In the next step, the electron pairs...

Preparation of Amines: Reduction of Amides and Nitriles 01:13

2.9K

Nitriles can be reduced to primary amines using reducing agents like lithium aluminum hydride or catalytic hydrogenation. The reduction introduces an amino group with an extra carbon in the skeleton. Nitriles are formed from the reaction between alkyl halides and sodium cyanide through the SN2 mechanism. Primary alkyl halides are the preferred substrates to prepare nitriles.
Amides can be reduced to primary, secondary, and tertiary amines using catalytic hydrogenation, active metals like Fe,...

Electrophilic Aromatic Substitution: Nitration of Benzene 01:20

8.0K

The nitration of benzene is an example of an electrophilic aromatic substitution reaction. It involves the formation of a very powerful electrophile, the nitronium ion, which is linear in shape. The reaction occurs through the interaction of two strong acids, sulfuric and nitric acid.

Sulfuric acid is stronger and protonates the nitric acid on the hydroxyl group, followed by loss of water molecule, generating the nitronium ion.

The nitronium ion acts as an electrophile that reacts with...

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

2.6K

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,...

Reduction of Alkynes to <em>cis</em>-Alkenes: Catalytic Hydrogenation 02:24

8.9K

Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.

Thermodynamic Stability
Catalytic hydrogenation reactions help evaluate the relative thermodynamic stability of hydrocarbons. For example, the heat of hydrogenation of acetylene is −176 kJ/mol, and that of ethylene is −137 kJ/mol. The higher exothermicity associated...

Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions 01:20

2.3K

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...