Consecutive reactions in the thermal decomposition of phenylalkyldiazirines

Abstract

. Can. J. Chem. 55,3596 (1977). The thermal decomposition of phenyl-n-butyldiazirine and of phenylmethyldiazirine in DMSO and in HOAc have been investigated over the temperature range 80-130°C. The intermediate diazo compounds, 1-phenyl-1-diazopentane and 1-phenyldiazoethane respectively have been detected and isolated. The decomposition of phenyl-n-butyldiazirine and the subsequent decomposition of its product, 1-phenyl-1-diazopentane, are an illustration of consecutive reactions. The kinetic parameters for the isomerization and decomposition reactions have been determined. The isomerization of phenylmethyldiazirine to 1-phenyldiazoethane is first order and probably unimolecular but the kinetics for the subsequent reactions of 1-phenyldiazoethane are complicated by several competing rate processes. Chem. 55,3596 (1977). On ttudie la dtcomposition thermique entre 80 et 130°C du phtnyl-3 n-butyl-3 diazirine et du phenyl-3 mtthyl-3 diazirine dans le DMSO et I'acide acttique. Les composts diazo intermtdiaires sont respectivemei~t le phtnyl-1 diazo-l pentane et le phenyl-1 diazo-1 tthane. Ces derniers ont t t t dktectts et isolts. La dtcomposition du phtnyl-3 n-butyl-3 diazirine et la dtcomposition ulttrieure de son intermtdiaire le phtnyl-1 diazo-1 pentane sont un bon exemple de rtactions successives. On determine les paramktres cinttiques pour les rtactions d'isomtrisation et de decomposition. L'isomtrisation du phtnyl-3 methyl-3 diazirine en phtnyl-1 diazo-1 tthane est d'ordre 1 et probablement unimoltculaire, mais les cinttiques des rtactions ulttrieures du phenyl-1 diazo-1 tthane sont compliqutes par plusieurs processus qui entrent en compttition.[Traduit par le journal]

Benzocyclobutadienyl Anion: Formation and Energetics of an Antiaromatic Molecule

“…The second strategy for synthesizing aryl substituted diaziridines (via a benzyl imine precursor) has been successfully applied to acetophenone and other alkyl-aryl ketones. 22,23 Proton NMR results suggest diaziridine 8 can be prepared from the benzyl imine of benzocyclobutenone. The product, however, was never isolated.…”

Effect of Substituents on the Thermal Decomposition of Diazirines: Experimental and Computational Studies

“…We determined the yields of C 60 CPhCl and C 60 Ad by HPLC analysis and the yields of C 60 CPh( n -Bu) and ( E )-1-pheny-1-pentene by 1 H NMR measurement of the reaction mixture. We synthesized phenylchlorodiazirine, phenyl- n -butyldiazirine, and 2-adamantane-2,3‘-[3 H ]diazirine by a previously reported procedure …”

One‐Pot Synthesis of Diazirines and 15N2‐Diazirines from Ketones, Aldehydes and Derivatives: Development and Mechanistic Insight

“…The three‐membered heterocyclic ring 3 H ‐diazirine (diazirine) is one of the rare chemical scaffolds able to generate a highly reactive species under an external stimulus such as light, heat, [1] or ultrasound [2] . This particular reactivity has been exploited in cross‐coupling reactions with aryl halides [3] or boronic acids, [4] and for the generation of sulfur ylides which are useful intermediates in synthetic chemistry [5] .…”