Catalytic Activity of Triphenylphosphine for Electrophilic Aromatic Bromination Using N-Bromosuccinimide and Process Safety Evaluation

IF 3.1 3区化学 Q2 CHEMISTRY, APPLIED Organic Process Research & Development Pub Date : 2024-10-02 DOI:10.1021/acs.oprd.4c00307

Masahiro Hosoya, Kenichi Ishibashi, Takafumi Ohara, Atsunori Mori, Kentaro Okano

引用次数: 0

Abstract

Electrophilic aromatic bromination using N-bromosuccinimide (NBS) is the most widely used reaction to synthesize highly functionalized aromatic compounds. We encountered catalytic activity of triphenylphosphine for aromatic bromination. This catalytic activity was successfully applied to a wide range of organic solvents and enabled the addition of NBS below the flash point of various organic solvents. Toward the industrial implementation of this bromination, we evaluated the process safety including the reaction heat and thermal decomposition. The analysis revealed that the characteristic behavior of the reaction heat made it difficult to suppress the increase of the internal temperature. However, precise evaluation of the reaction heat suggested the sequential addition of NBS. This procedure suppressed the increase of the internal temperature below 5 °C, which made the industrial implementation of this bromination feasible with process safety.

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三苯基膦对 N-溴代丁二酰亚胺亲电芳香族溴化反应的催化活性及工艺安全性评估

使用 N-溴代丁二酰亚胺（NBS）进行亲电芳香溴化反应是合成高官能度芳香化合物最广泛使用的反应。我们发现三苯基膦对芳香溴化反应具有催化活性。这种催化活性成功地应用于多种有机溶剂，并使 NBS 的添加温度低于各种有机溶剂的闪点。为了实现这种溴化反应的工业化，我们对包括反应热和热分解在内的工艺安全性进行了评估。分析表明，由于反应热的特性，很难抑制内部温度的升高。然而，对反应热的精确评估建议依次添加 NBS。这一步骤将内部温度的升高抑制在 5 ℃ 以下，从而在保证工艺安全的前提下实现了工业化溴化。

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来源期刊

Organic Process Research & Development 化学-应用化学

CiteScore

6.90

自引率

14.70%

发文量

251

审稿时长

2 months

期刊介绍： The journal Organic Process Research & Development serves as a communication tool between industrial chemists and chemists working in universities and research institutes. As such, it reports original work from the broad field of industrial process chemistry but also presents academic results that are relevant, or potentially relevant, to industrial applications. Process chemistry is the science that enables the safe, environmentally benign and ultimately economical manufacturing of organic compounds that are required in larger amounts to help address the needs of society. Consequently, the Journal encompasses every aspect of organic chemistry, including all aspects of catalysis, synthetic methodology development and synthetic strategy exploration, but also includes aspects from analytical and solid-state chemistry and chemical engineering, such as work-up tools，process safety, or flow-chemistry. The goal of development and optimization of chemical reactions and processes is their transfer to a larger scale; original work describing such studies and the actual implementation on scale is highly relevant to the journal. However, studies on new developments from either industry, research institutes or academia that have not yet been demonstrated on scale, but where an industrial utility can be expected and where the study has addressed important prerequisites for a scale-up and has given confidence into the reliability and practicality of the chemistry, also serve the mission of OPR&D as a communication tool between the different contributors to the field.