933-21-1Relevant academic research and scientific papers
TERMINATION REACTIONS OF C5-C12 CYCLOALKYL RADICALS AND CARBENES
Wojnarovits, Laszlo
, p. 1449 - 1452 (2007/10/02)
Reactions of C5-C12 cycloalkyl radicals and carbenes produced during radiolysis, vacuum-u.v. photolysis, and decomposition of cycloalkanone p-tosylhydrazones were investigated.The disproportionation to combination ratios of radicals are ca. 1 and agree with the ratios of linear secondary radicals.The disproportionation smaller cycloalkyl radicals yields cis-cycloalkenes and cycloalkanes; from C9 and C10 cis- and trans-cycloalkenes and cycloalkanes and from C11 and C12 trans-cycloalkenes and cycloalkanes are produced.Both atoms of H2 given off in the elimination reaction from excited cycloalkane molecules orginate from the same carbon atom and in this process carbenes are formed.Rearrangement of small (C5, C6) and large (C11, C12) cycloalkylcarbenes in the solvent of the given cycloalkane occurs by 1,2-hydrogen migration.C7-C10 carbenes rearrange both by hydrogen atom migration and transannular insertion.
Deamination Reactions, 37. Decomposition of Bicyclononane- and Bicyclonon-2-ene-9-diazonium Ions
Kirmse, Wolfgang,Hellwig, Georg
, p. 2744 - 2754 (2007/10/02)
Bicyclononane-exo-9-diazonium ions (9) have been generated from the corresponding nitrosourea (8) and base.In weakly alkaline solution (E)-3-methoxycyclononene (11) was formed by disrotatory ring opening of (9).In the presence of sodium methoxide 1,2-cyclononadiene (13) and exo-9-methoxybicyclononane (15) were additional products, presumably arising via carbene 12.Bicyclonon-2-ene-exo-9-diazonium ions (21) decomposed without participation of the double bond to give the (Z,E)-methoxycyclononadienes 22 and 23.The 21-derived carbene 29 afforded the bicyclic ether 30 and the elusive 1,2,4-cyclononatriene (32).In contrast to its lower homologs, 29 did not undergo a carbene-carbene rearrangement (29 -> 31).
