Thermal Hazard Evaluation and Safety Considerations for the Use of O-Benzoyl-N-alkyl Hydroxylamines as Synthetic Reagents

IF 3.5 3区 化学 Q2 CHEMISTRY, APPLIED
Joseph J. Topczewski, Hayden Cheek, Joseph M. Gruber, Brett M. Marsh, Daniel J. Valco
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引用次数: 0

Abstract

Numerous synthetic methods utilize O-benzoyl-N-alkyl hydroxylamines (BzO-NR2) as electrophilic aminating reagents. The need for gram scale quantities of these reagents prompted a detailed reactive chemistry evaluation. This report provides information on the thermal hazards associated with this class of BzO-NR2 reagent. Several of these reagents demonstrated low detected onset temperatures, as determined by differential scanning calorimetry (DSC). The observed detected onset temperature was below the reported operating temperatures for some synthetic methods. Variable scan rate DSC data indicated a high probability of autocatalytic decomposition. These data were modeled by using Advanced Kinetics and Technology Solutions (AKTS) software to predict and confirm autocatalytic behavior. Accelerating rate calorimetry (ARC) was performed to confirm the low thermal onset, high exotherm, and gas generation of the decomposition. Finally, micro reaction calorimetry and analytical methods were used to confirm the initial steps of the decomposition pathway. Taken together, these results indicate that care should be taken in the synthesis, use, transport, and storage of these reagents.

Abstract Image

邻苯甲酰- n -烷基羟胺合成试剂的热危害评价及安全性考虑
许多合成方法利用邻苯甲酰- n -烷基羟胺(BzO-NR2)作为亲电胺化试剂。对这些试剂的克级数量的需求促使进行了详细的反应化学评价。本报告提供了与这类BzO-NR2试剂相关的热危害信息。根据差示扫描量热法(DSC)的测定,这些试剂中有几种表现出较低的检测起始温度。观察到的检测起始温度低于一些合成方法报告的操作温度。变扫描率DSC数据表明自催化分解的可能性很大。这些数据通过高级动力学和技术解决方案(AKTS)软件建模,以预测和确认自催化行为。采用加速速率量热法(ARC)证实了低热启动、高放热和气体生成的分解。最后,采用微反应量热法和分析方法确定了分解途径的初始步骤。综上所述,这些结果表明在合成、使用、运输和储存这些试剂时应谨慎。
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来源期刊
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.
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