Hydrazoic Acid and Azides

Bräse, Stefan; Mende, Marco; Jobelius, Horst H.; Scharf, Hans‐Dieter

doi:10.1002/14356007.a13_193.pub2

Cited by 6 publications

(5 citation statements)

References 69 publications

(78 reference statements)

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“…Furthermore, studies probing the reaction variables in the presence of a minimum catalytic amount of proton source are summarized in Table . This is especially relevant as it impacts the potential production of incipient hydrazoic acid during the reaction . The screening of the reaction as a function of temperature indicates that isolated yields increase from 20% at 50 °C to 85% at 75 °C to finally plateaue at 91–93% from 80 to 90 °C.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of 5-Substituted Tetrazoles: Reaction of Azide Salts with Organonitriles Catalyzed by Trialkylammonium Salts in Non-polar Media

Chand

Gelbaum

Griffith³

et al. 2022

Org. Process Res. Dev.

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An efficient synthesis of 5-substituted tetrazole derivatives via the addition of azide ions to an organonitrile is presented. This new protocol minimizes the potential generation of hydrazoic acid by employing a catalytic amount of an activating proton source (trialkylammonium chloride) in combination with a phase transfer agent (tetraalkylammonium salt). Both aromatic and aliphatic nitriles are successfully reacted to produce the corresponding 5-substituted-1H-tetrazole products. The superiority of choline chloride as a phase transfer agent, the recyclability of both the catalytic proton source and the phase transfer agent, and the proposed mechanistic role of each of the reaction components are also presented.

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Section: Resultsmentioning

confidence: 99%

Synthesis of 5-Substituted Tetrazoles: Reaction of Azide Salts with Organonitriles Catalyzed by Trialkylammonium Salts in Non-polar Media

Chand

Gelbaum

Griffith³

et al. 2022

Org. Process Res. Dev.

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“…All articles describing human azide exposure were included. Reports of physical trauma due to airbag deployment alone were excluded as were articles on azides other than sodium, since NaN 3 is the principal azide species produced and it is available for purchase online [ 2 , 20 , 21 ]. Finally, we excluded articles that were duplicated cases, had insufficient data, or irrelevant account, such as no discussion of human azide poisoning.…”

Section: Methodsmentioning

confidence: 99%

Sodium azide poisoning: a narrative review

Tat

Heskett

Satomi

et al. 2021

Clinical Toxicology

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Context: Sodium azide is a highly toxic chemical. Its production has increased dramatically over the last 30 years due to its widespread use in vehicular airbags, and it is available for purchase online. Thus, accidental exposure to azide or use as a homicidal or suicidal agent could be on the rise, and secondary exposure to medical personnel can occur. No antidote exists for azide poisoning. We conducted a systematic review of azide poisoning to assess recent poisoning reports, exposure scenarios, clinical presentations, and treatment strategies. Methods: We searched both medical and newspaper databases to review the literature between 01/ 01/2000 and 12/31/2020, pairing the controlled vocabulary and keyword terms "sodium azide" or "hydrazoic acid" with terms relating to exposures and outcomes, such as "ingestion," "inhalation," "exposure," "poisoning," and "death." We included all peer-reviewed papers and news articles describing human azide poisoning cases from English and non-English publications that could be identified using English keywords. Data abstracted included the number, age, and gender of cases, mode of exposure, exposure setting, azide dose and route of exposure, symptoms, outcome, and treatment modalities. Results: We identified 663 peer-reviewed papers and 303 newspaper articles. After removing duplicated and non-qualifying sources, 54 publications were reviewed describing 156 cases, yielding an average of 7.8 reported azide poisoning cases per year. This rate is three times higher than in a previous review covering the period of 1927 to 1999. Poisoning occurred most commonly in laboratory workers, during secondary exposure of medical personnel, or from a ripped airbag. Hypotension occurred commonly, in some cases requiring vasopressors and one patient received an intra-aortic ballon pump. Gastric lavage and/or activated charcoal were used for oral azide ingestion, and sodium nitrite, sodium thiosulfate, and/or hydroxocobalamin were used in severely poisoned patients. Conclusions: Recent increases in azide poisoning reports may stem from greater commercial use and availability. Treatment of systemic poisoning may require aggressive hemodynamic support due to profound hypotension. Based on mechanistic considerations, hydroxocobalamin is a rational choice for treating azide poisoning.

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“…These methodologies demonstrate the chemical stability and tractability of the vinyl sulfoximine motif, and one such recent study has given rise to the first examples of bioactive vinyl sulfoximines that are thought to activate the transcription factor nuclear factor erythroid 2-related factor 2 (Nrf2), although a covalent mechanism of action was not proposed . However, these synthetic routes have clear limitations; they generally utilize multiple-step sequences that are reliant on the use of hydrazoic acid or O -(mesitylenesulfonyl)hydroxylamine (MSH) for sulfoxide imidation, both of which are known for their thermal instability. , There are very few examples of terminal vinyl sulfoximines or enantioenriched vinyl sulfoximines. Moreover, the first two examples of vinyl sulfonimidamides were only reported very recently, despite the prevalence of the analogous vinyl sulfonamides, which we attribute to the historically limited synthetic methodology regarding sulfonimidamides.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Configurational Assignment of Vinyl Sulfoximines and Sulfonimidamides

et al. 2021

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Vinyl sulfones and sulfonamides are valued for their use as electrophilic warheads in covalent protein inhibitors. Conversely, the S(VI) aza-isosteres thereof, vinyl sulfoximines and sulfonimidamides, are far less studied and have yet to be applied to the field of protein bioconjugation. Herein, we report a range of different synthetic methodologies for constructing vinyl sulfoximine and vinyl sulfonimidamide architectures that allows access to new areas of electrophilic chemical space. We demonstrate how late stage functionalization can be applied to these motifs to incorporate alkyne tags, generating fully functionalized probes for future chemical biology applications. Finally, we establish a workflow for determining the absolute configuration of enantioenriched vinyl sulfoximines and sulfonimidamides by comparing experimentally and computationally determined electronic circular dichroism spectra, enabling access to configurationally assigned enantiomeric pairs by separation. File list (2) download file view on ChemRxiv S&C Vinyl S(VI) ChemRxiv.pdf (2.21 MiB) download file view on ChemRxiv Supplementary S&C Vinyl S(VI) .pdf (15.81 MiB)

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Hydrazoic Acid and Azides

Cited by 6 publications

References 69 publications

Synthesis of 5-Substituted Tetrazoles: Reaction of Azide Salts with Organonitriles Catalyzed by Trialkylammonium Salts in Non-polar Media

Synthesis of 5-Substituted Tetrazoles: Reaction of Azide Salts with Organonitriles Catalyzed by Trialkylammonium Salts in Non-polar Media

Sodium azide poisoning: a narrative review

Synthesis and Configurational Assignment of Vinyl Sulfoximines and Sulfonimidamides

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