より安全な爆発反応の代替法(Safer alternative for an explosive reaction)

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2024-02-29 マックス・プランク研究所

化学業界では140年以上もの間、爆発的に反応するアリルジアゾニウム塩がペンキ製造などに使用されてきましたが、マックス・プランク石炭研究所のチームがこれらの化学物質を使用するプロセスにおいてより安全な代替方法を発見しました。この新しい方法では、植物が硝酸を還元する反応を模倣し、化学業界が肥料製造に使用する化学物質を活用しています。これにより、プロセスがよりコスト効率よくなる可能性があります。また、新しいプロトコルでは複数のステップを組み合わせることで、危険物質の大量発生を避けることができ、科学的にも新しい化学的アプローチが可能となります。

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硝酸塩還元がより安全なアリルジアゾニウム合成を可能にする Nitrate reduction enables safer aryldiazonium chemistry

JAVIER MATEOS, TIM SCHULTE, DEEPAK BEHERA, MARKUS LEUTZSCH, […], AND TOBIAS RITTER
Science  Published:25 Apr 2024
DOI:https://doi.org/10.1126/science.adn7006

Editor’s summary

The Sandmeyer reaction is one of the oldest in organic chemistry, and, remarkably, it is still widely practiced in much the same way that it was reported in the 19th century. The reaction appends a variety of substituents onto aryl rings by first generating highly reactive diazonium leaving groups. With this reactivity comes explosion risk, however. Mateos et al. report a safer variation that avoids diazonium accumulation. By steadily producing small quantities of these reactive intermediates just before displacement, the authors achieved the same outcome at much lower risk. —Jake S. Yeston

Abstract

Aryldiazonium salts remain a staple in organic synthesis and are still prepared largely in accord with the protocol developed in the 19th century. Because of the favorable reactivity that often cannot be achieved with other aryl(pseudo)halides, diazonium chemistry continues to grow. Facile extrusion of dinitrogen contributes to the desired reactivity but is also reason for safety concerns. Explosions have occurred since the discovery of these reagents and still result in accidents. In this study, we report a diazonium chemistry paradigm shift based on nitrate reduction using thiosulfate or dihalocuprates as electron donors that avoids diazonium accumulation. Because nitrate reduction is rate-limiting, aryldiazoniums are produced as fleeting intermediates, which results in a safer and often more efficient deaminative halogenation in a single step from anilines.

0500化学一般
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