Despite their wide use in academia as metal-carbene precursors, diazo compounds are often avoided in industry owing to concerns over their instability, exothermic decomposition, and potential explosive behavior. The stability of sulfonyl azides and other diazo transfer reagents is relatively well understood, but there is little reliable data available for diazo compounds. This work first collates available sensitivity and thermal analysis data for diazo transfer reagents and diazo compounds to act as an accessible reference resource. Thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and accelerating rate calorimetry (ARC) data for the model donor/acceptor diazo compound ethyl (phenyl)diazoacetate are presented. We also present a rigorous DSC dataset with 43 other diazo compounds, enabling direct comparison to other energetic materials to provide a clear reference work to the academic and industrial chemistry communities. Interestingly, there is a wide range of onset temperatures (T onset) for this series of compounds, which varied between 75 and 160 °C. The thermal stability variation depends on the electronic effect of substituents and the amount of charge delocalization. A statistical model is demonstrated to predict the thermal stability of differently substituted phenyl diazoacetates. A maximum recommended process temperature (T D24) to avoid decomposition is estimated for selected diazo compounds. The average enthalpy of decomposition (ΔH D) for diazo compounds without other energetic functional groups is -102 kJ mol-1. Several diazo transfer reagents are analyzed using the same DSC protocol and found to have higher thermal stability, which is in general agreement with the reported values. For sulfonyl azide reagents, an average ΔH D of -201 kJ mol-1 is observed. High-quality thermal data from ARC experiments shows the initiation of decomposition for ethyl (phenyl)diazoacetate to be 60 °C, compared to that of 100 °C for the common diazo transfer reagent p-acetamidobenzenesulfonyl azide (p-ABSA). The Yoshida correlation is applied to DSC data for each diazo compound to provide an indication of both their impact sensitivity (IS) and explosivity. As a neat substance, none of the diazo compounds tested are predicted to be explosive, but many (particularly donor/acceptor diazo compounds) are predicted to be impact-sensitive. It is therefore recommended that manipulation, agitation, and other processing of neat diazo compounds are conducted with due care to avoid impacts, particularly in large quantities. The full dataset is presented to inform chemists of the nature and magnitude of hazards when using diazo compounds and diazo transfer reagents. Given the demonstrated potential for rapid heat generation and gas evolution, adequate temperature control and cautious addition of reagents that begin a reaction are strongly recommended when conducting reactions with diazo compounds.

中文翻译：

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重氮化合物和重氮转移试剂的热稳定性和爆炸危险性评估。

尽管重氮化合物在学术界广泛用作金属卡宾的前体，但由于对重氮化合物的不稳定性，放热分解和潜在的爆炸行为的担忧，在工业上仍经常避免使用重氮化合物。相对而言，磺酰叠氮化物和其他重氮转移试剂的稳定性是众所周知的，但重氮化合物的可靠数据很少。这项工作首先整理重氮转移试剂和重氮化合物的可用灵敏度和热分析数据，以作为可访问的参考资源。给出了模型供体/受体重氮化合物（苯基）重氮乙酸乙酯的热重分析（TGA），差示扫描量热法（DSC）和加速速率量热法（ARC）数据。我们还提供了严格的DSC数据集，其中包含其他43种重氮化合物，可以直接与其他高能材料进行比较，从而为学术和工业化学界提供清晰的参考资料。有趣的是，这一系列化合物的起始温度（T起始）范围很广，在75至160°C之间变化。热稳定性变化取决于取代基的电子效应和电荷离域的量。统计模型可以预测不同取代的重氮苯基乙酸酯的热稳定性。为选定的重氮化合物估算了避免分解的最高推荐过程温度（TD24）。没有其他高能官能团的重氮化合物的平均分解焓（ΔHD）为-102 kJ mol-1。使用相同的DSC协议分析了几种重氮转移试剂，发现它们具有更高的热稳定性，这与所报道的值总体上是一致的。对于磺酰叠氮化物试剂，观察到的平均ΔHD为-201 kJ mol-1。ARC实验获得的高质量热数据表明，重氮（苯基）乙酸乙酯的分解起始温度为60°C，而普通重氮转移试剂对乙酰氨基苯磺酰叠氮化物（p-ABSA）的分解起始温度为100°C。将吉田相关性应用于每种重氮化合物的DSC数据，以提供其冲击敏感性（IS）和爆炸性的指示。作为一种纯净物质，预计没有一种重氮化合物具有爆炸性，但是许多（特别是供体/受体重氮化合物）被认为对撞击敏感。因此，建议对纯净的重氮化合物进行操作，搅拌和其他处理时要格外小心，以免产生影响，尤其是在大量使用时。提供了完整的数据集，以告知化学家使用重氮化合物和重氮转移试剂时危险的性质和严重程度。考虑到已证明的快速生热和放出气体的潜力，强烈建议在与重氮化合物进行反应时，适当控制温度并谨慎添加可开始反应的试剂。