The decomposition of .beta.-phenethylsulfonyl azides. Solution chemistry and flash vacuum pyrolysis

Abramovitch, R. A.; Holcomb, William D.; Wake, Shigeo

doi:10.1021/ja00396a039

Cited by 24 publications

(7 citation statements)

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“…As indicated by early chemical trapping reactions ,,− and very recent ultrafast ,, and matrix-isolation spectroscopy studies, − ,, the decomposition of sulfonyl azides is very different to that of the structurally related carbonyl azides. Specifically, the key sulfonyl nitrene intermediates seem to be much more rigid than carbonyl nitrenes so that only very few cases of the pseudo-Curtius rearrangement have been clearly established.…”

Section: Discussionmentioning

confidence: 99%

Methanesulfonyl Azide: Molecular Structure and Photolysis in Solid Noble Gas Matrices

Deng

et al. 2016

J. Phys. Chem. A

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The parent sulfonyl azide CH3SO2N3 has been characterized in a neat form by IR (gas, matrix-isolation) and Raman (solid) spectroscopy, and its structure has been established by X-ray crystallography. In both gas phase and solid state, the azide exhibits single conformation with the azido ligand being synperiplanar to one of the two S═O groups. In the crystal molecules of CH3SO2N3 are interconnected through three-dimensional O···H-C-H···O hydrogen bonds. Upon an ArF laser (193 nm) photolysis, the azide in solid noble gas matrices splits off N2 and yields the sulfonyl nitrene CH3SO2N in the triplet ground state. Subsequent photolysis with UV light (266 nm) causes the transformation from the nitrene to the pseudo-Curtius rearrangement product CH3NSO2. The identification of the photolysis intermediates by matrix-isolation IR spectroscopy is supported by quantum chemical calculations with DFT methods.

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Section: Discussionmentioning

confidence: 99%

Methanesulfonyl Azide: Molecular Structure and Photolysis in Solid Noble Gas Matrices

Deng

et al. 2016

J. Phys. Chem. A

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“…FVP of β-phenethylsulfonyl azides at ∼300 °C (0.1–4 hPa) again resulted in nitrene cyclization onto the phenyl ring to yield the sultam 369 in up to 19% yield together with a variety of rearrangement products (eq ). In further work, seven-membered ring sultams 371 were obtained in yields of 23–27% by FVP of aralkylsulfonyl azides 370 (eq ). The mesityl derivative 372 afforded an 88% yield of the sultam 373 , where a methyl group shift has occurred (eq 68 ).…”

Section: Azidesmentioning

confidence: 99%

Flash Vacuum Pyrolysis of Azides, Triazoles, and Tetrazoles

2017

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Flash vacuum pyrolysis (FVP) of azides is an extremely valuable method of generating nitrenes and studying their thermal rearrangements. The nitrenes can in many cases be isolated in low-temperature matrices and observed spectroscopically. NH and methyl, alkyl, aralkyl, vinyl, cyano, aryl and N-heteroaryl, acyl, carbamoyl, alkoxycarbonyl, imidoyl, boryl, silyl, phosphonyl, and sulfonyl nitrenes are included. FVP of triazoloazines generates diazomethylazines and azinylcarbenes, which often rearrange to the energetically more stable arylnitrenes. N elimination from monocyclic 1,2,3-triazoles can generate iminocarbenes, 1H-azirines, ketenimines, and cyclization products, and 1,2,4-triazoles are precursors of nitrile ylides. Benzotriazoles are preparatively useful precursors of cyanocyclopentadienes, carbazoles, and aza-analogues. FVP of 5-aryltetrazoles can result in double N elimination with formation of arylcarbenes or of heteroarylcarbenes, which again rearrange to arylnitrenes. Many 5-substituted and 2,5-disubstituted tetrazoles are excellent precursors of nitrile imines (propargylic, allenic, or carbenic), which are isolable at low temperatures in some cases (e.g., aryl- and silylnitrile imines) or rearrange to carbodiimides. 1,5-Disubstituted tetrazoles are precursors of imidoylnitrenes, which also rearrange to carbodiimides or add intramolecularly to aryl substituents to yield indazoles and related compounds. Where relevant for the mechanistic understanding, pyrolysis under flow conditions or in solution or the solid state will be mentioned. Results of photolysis reactions and computational chemistry complementing the FVP results will also be mentioned in several places.

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“…Aqueous acid hydrolysis liberated phosphonic acid 21 and treatment with s-trioxane gave polymer 11. The sulfonic acid polymer 12 was prepared (Scheme 1) starting with 2-(4-benzyloxyphenyl)ethanol (22) [39]. Conversion of 22 to bromide 23 using CBr4 and triphenylphosphine [40] and subsequent treatment with Na2S03 [41] gave 24 in 20% overall yield. The sulfonate 24 was esterified (SOC1I, ethanol) to achieve solubility and furnished 25.…”

Section: Chemistrymentioning

confidence: 99%

Mimicry of Biological Macromolecules by Polyaromatic Anionic Compounds

Regan¹,

Bruno²,

Chang³

et al. 1993

Journal of Bioactive and Compatible Polymers

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The preparation, characterization and biological properties of some polyanionic polymers are reported. These polymers are constructed with repeating phenol-based monomers. The anionic groups attached to the aromatic nucleus provide the basis for binding to basic domains of proteins. Scaf-*Author to whom correspondence should be addressed.at CARLETON UNIV on June 21, 2015 jbc.sagepub.com Downloaded from 318 fold flexibility permits the polyanionic polymers to adopt low energy conformations suitable for interacting with coagulation proteins and an anti-DNA monoclonal antibody. Structure activity relationships (SAR) and comparisons with aurintricarboxylic acid are described. The polymers doubled the clotting time in the APTT assay with value ranging from 10-1000 μg/mL. Binding to an anti-DNA monoclonal antibody occurred with ICso values of 0.3-5.0 μg/mL. INTRODUCTIOÑ

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The decomposition of .beta.-phenethylsulfonyl azides. Solution chemistry and flash vacuum pyrolysis

Cited by 24 publications

References 0 publications

Methanesulfonyl Azide: Molecular Structure and Photolysis in Solid Noble Gas Matrices

Methanesulfonyl Azide: Molecular Structure and Photolysis in Solid Noble Gas Matrices

Flash Vacuum Pyrolysis of Azides, Triazoles, and Tetrazoles

Mimicry of Biological Macromolecules by Polyaromatic Anionic Compounds

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