10568-85-1Relevant academic research and scientific papers
BEHAVIOUR OF CYCLOPROPANES BEARING CAPTO-DATIVE SUBSTITUTION UPON ELECTRON-IMPACT AND FLASH-VACUUM PYROLYSIS CONDITIONS
Chen, Lin-Zhi,Flammang, Robert,Maquestiau, Andre,Masamba, Wayiza,Merenyi, Robert,et al.
, p. 529 - 546 (2007/10/02)
Tandem mass spectrometry has been applied to investigate the behaviour of bis-captodative(cd) substituted cyclopropanes upon electron impact (EI) and flash-vacuum pyrolysis (FVP) comditions.Ring-opening of the molecular ions of 1 followed by a 1,2-hydrogen shift preceedes the fragmentation consisting mainly in the competitive losses of CH3S. and CH2S.The least energy demanding reaction is however a methyl loss requiring also ring cleavage.The m/z 70 base peak is ascribed to cyanothioacylium ions(NC-C=S(1+)) as indicated by the characteristic fragmentations induced by collision.Upon FVP conditions 1 decays to the cd olefin 8 and the carbene 9 in competition with the extrusion of CH3S. and CH3. radicals at the highest temperatures.The behaviour of 2 upon both conditions is dominated by the chemistry of the t-butyl substituents.Ring cleavage of the molecular ions of 3 preceedes also the fragmentation and induces rearrangement reactions yielding unexpected cyclohexadiene thione ions and C7H7(1+) ions.Upon FVP, C-S bond homolysis readily occurs in competition with an elimination of a carbene molecule.
