Mechanism of the thermal decomposition of vinyl azides

L'abbé, G.; Mathys, Georges

doi:10.1021/jo00925a047

Cited by 48 publications

(21 citation statements)

References 2 publications

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“…As has been established in our current research, trans-vinyldiazo compounds H-1, similarly to the parent vinyldiazomethane, 19 very easily undergo intramolecular ring closure to produce pyrazoles 3 (Scheme 2). At the same time, cis-vinyldiazocarbonyl compounds H-2 were found to be much more inert than trans-stereoisomers 1 in this reaction (Scheme 4).…”

Section: Mechanistic Outlooksupporting

confidence: 52%

“…1 H, 13 C and 19 F NMR spectra were recorded on 200, 300, 600 MHz ( 1 H), 50, 75, 150 MHz ( 13 C), 188, 282 MHz ( 19 F) and at 81 MHz ( 31 P) in CDCl 3 solution using TMS, CHCl 3 or H 3 PO 4 as internal standards. All reactions were carried out in carefully purified and dried solvents and were monitored by thinlayer chromatography (TLC) using UV light and iodine as visualizing agents.…”

Section: General Methodsmentioning

confidence: 99%

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Effect of configuration of 2-vinyldiazocarbonyl compounds on their reactivity: experimental and computational study

et al. 2014

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Non-fluorinated vinyldiazo compounds with trans-configuration irrespective of the nature of 3-R(1)-substituent (R(1) = H, Me, TBSO) even under ambient conditions easily cyclize to produce pyrazoles, while cis-stereoisomers undergo similar ring closure only at elevated temperatures or decompose to produce vinyloxocarbene reaction products. The 3-CF3-substituted analogues with cis- or trans-configuration do not produce pyrazoles at all, but on heating furnish only vinylcarbene derived products. DFT calculations of theoretical energy barriers adequately explain the different experimental reactivity found for stereoisomeric vinyldiazocarbonyl compounds, and a new model for their interconversion through the corresponding pyrazoles has been suggested.

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Section: Mechanistic Outlooksupporting

confidence: 52%

Section: General Methodsmentioning

confidence: 99%

Effect of configuration of 2-vinyldiazocarbonyl compounds on their reactivity: experimental and computational study

et al. 2014

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“…12 (2) However, in the case of vinyl azides, calculations have suggested that the formation of azirines from vinyl azides involves either rate determining formation of vinyl nitrenes with no activation energy for the conversion of the nitrene to the azirine or that azirines are formed from vinyl azides via a concerted losss of nitrogen. 15 We report herein the synthesis of vinyl azide 1 and its thermolysis under a variety of conditions in the presence of water, methyl alcohol, t-butyl alcohol, t-butylamine, and t-butyl mercaptan. 14 In addition, Hassner's work also suggests that these conclusions may not be general, and the mechanism for the decomposition of an azide will depend on the nature of the substituents.…”

Section: Resultsmentioning

confidence: 99%

A Thio-Staudinger Reaction: Thermolysis of a Vinyl Azide in the Presence of t -Butyl Mercaptan

Sauers

Arnum

2003

Phosphorus, Sulfur, and Silicon and the Related Elements

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The thermal decomposition of E-3-azido-3-hexene-2,5-dione (1) in protic media gave rise to several novel reactions of the azide 1 including adducts derived from keteneimine 11. Reaction with t-butyl mercaptan yielded two products, keteneimine-derived mercaptan addition product 20 and a sulfenimine 6. Trapping of a vinyl nitrene intermediate or a thio-Staudinger reaction was considered as a possible mechanism for the formation of sulfenimine 6. The absence of the vinyl nitrene addition products 3 and 5 when the thermal decomposition was conducted in either methanol or t-butylamine suggests a thio-Staudinger reaction is operative.

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“…There are three mechanisms that have been proposed for the reaction ( a‐c ). A combined mechanism (Scheme 26, Path a ) [43] has been proposed by L'abbé et al to be energetically plausible [44], while a pathway including a singlet vinyl nitrene (Scheme 26, Path b ) was found to be of higher energy [15g,45]. The path (a) is a concerted mechanism in which elimination of N 2 is simultaneous with the ring closure through a transition state ( 2 ).…”

Section: Decomposition Of Vinyl Azidesmentioning

confidence: 99%

Synthesis of various functionalized 2H‐azirines: An updated library

Majee

2021

Journal of Heterocyclic Chem

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In the current extensive review, we pay special attention to the progress in the synthesis of 2H‐azirine. Content is organized by several main approaches for the synthesis of 2H‐azirines such as‐ Neber rearrangement, decomposition of vinyl azides, oxidative cyclization of enamines, ring contraction of isoxazoles or oxazaphospholes, radical addition/cyclization of alkynes, Swern oxidation or elimination reactions of aziridine derivatives, catalytic decomposition of α‐oximino diazo compounds, addition of silyldibromomethyllithium compounds to nitriles, addition of carbenes to nitriles and via azirine‐azirine transformations. Some of these approaches open up access to new 2H‐azirine derivatives and make the already established compounds more convenient. A description of these methods and the progress of using well‐known reactions leading to the aziridine system are presented in this section. This review surveys the progress of various functionalized 2H‐azirine formation reactions from the exploration period to the present.

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Mechanism of the thermal decomposition of vinyl azides

Cited by 48 publications

References 2 publications

Effect of configuration of 2-vinyldiazocarbonyl compounds on their reactivity: experimental and computational study

Effect of configuration of 2-vinyldiazocarbonyl compounds on their reactivity: experimental and computational study

A Thio-Staudinger Reaction: Thermolysis of a Vinyl Azide in the Presence of t -Butyl Mercaptan

Synthesis of various functionalized 2H‐azirines: An updated library

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