4‐Dodecylbenzenesulfonyl Azides

Hazen, George G.; Bollinger, F. W.; Roberts, F. E.; Russ, W.; Seman, J. J.; Staskiewicz, Steven J.

doi:10.1002/0471264180.os073.15

Cited by 6 publications

(6 citation statements)

References 12 publications

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“…Diazidomethane, CH 2 (N 3 ) 2 , conversely exhibits a strong propensity to explode . Fifteen years ago, the inadvertent formation of this substance by the reaction of sodium azide with dichloromethane (DCM) was implicated in laboratory explosions that typically occurred during solvent evaporation. , The danger of pairing ionic azides with polyhalomethanes has since been acknowledged, and alternative reaction media have been proposed including MeCN, – MeNO 2 , , DME, toluene, acetone, , and water (with or without adjuvants). – Even so, accidents of this nature continue to happen, and their causative agent is not universally recognized…”

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confidence: 99%

“…5,6 The danger of pairing ionic azides with polyhalomethanes has since been acknowledged, and alternative reaction media have been proposed including MeCN, [7][8][9][10] MeNO 2 , 10,11 DME, 12 tolu-ene, 13 acetone, 14,15 and water (with or without adjuvants). [16][17][18] Even so, accidents of this nature continue to happen, and their causative agent is not universally recognized. 19 Herein we describe an explosion that occurred several years ago in the course of the reaction sequence of eq 1, which was carried out in a kilo laboratory using conventional glassware.…”

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confidence: 99%

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Diazidomethane Explosion

Conrow

Dean

2008

Org. Process Res. Dev.

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confidence: 99%

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confidence: 99%

Diazidomethane Explosion

Conrow

Dean

2008

Org. Process Res. Dev.

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“…Cyclodehydration of microgel-bound 9 to the corresponding oxazoles 10 was performed using a modified Wipf procedure . However, in analogy to our solid-phase oxazole synthesis, slightly better yields and product purities were observed when recently introduced Burgess' reagent mediated cyclodehydration conditions were employed .…”

Section: Resultsmentioning

confidence: 99%

Preparation of New Microgel Polymers and Their Application as Supports in Organic Synthesis

2002

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A series of soluble microgel polymers have been synthesized using solution-phase polymerization reactions. In a systematic manner, several variables such as monomer concentration, cross-linker content, reaction solvent and reaction time were examined, and this provided an optimal polymer with both solubility and precipitation characteristics suitable for synthetic applications. Thus, a chemically functionalized microgel polymer was synthesized, and the utility of this polymer in the synthesis of a small array of oxazole compounds has been demonstrated. The advantage of the microgel polymers produced was that they exhibited solution viscosities lower than those of conventional linear polymers even at higher concentrations, and this was found to be beneficial for their precipitation properties. Compounds prepared using the described microgel polymer supports were obtained in similar yields and purity when compared with insoluble resins, and more importantly, the soluble polymer bound intermediates could be analyzed at each step using standard NMR techniques.

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“…Sulfonyl azides have been reported to be impact-sensitive; 62−64 however, another report claimed that impurities were the cause, i.e., pure MsN 3 was not impact-sensitive but a slightly impure sample was highly sensitive. 67 Pure TsN 3 has been reported to explode, 57,58 but the root cause of these incidents was not conclusively demonstrated to be the azide, and the only report of explosive power comes from an unpublished private correspondence. 62 It has been noted that preparations of sulfonyl azide using an alcohol as solvent lead to impurities, which may be the cause of the observed impact sensitivity, and so, the preparation of sulfonyl azides in acetone/water is recommended to avoid this possibility.…”

Section: ■ Introductionmentioning

confidence: 99%

Thermal Stability and Explosive Hazard Assessment of Diazo Compounds and Diazo Transfer Reagents

Green

Wheelhouse

Payne

et al. 2019

Org. Process Res. Dev.

230

218

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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.

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4‐Dodecylbenzenesulfonyl Azides

Abstract: 4‐dodecylbenzenesulfonyl azides product: dodecylbenzenesulfonyl azides

Cited by 6 publications

References 12 publications

Diazidomethane Explosion

Diazidomethane Explosion

Preparation of New Microgel Polymers and Their Application as Supports in Organic Synthesis

Thermal Stability and Explosive Hazard Assessment of Diazo Compounds and Diazo Transfer Reagents

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