51566-98-4Relevant articles and documents
Bridgehead carbocations via carbene fragmentation: Erasing a 1010 kinetic preference
Moss, Robert A.,Zheng, Fengmei,Fede, Jean-Marie,Ma, Yan,Sauers, Ronald R.,Toscano, John P.,Showalter, Brett M.
, p. 5258 - 5259 (2007/10/03)
1-Norbornyloxychlorocarbene (1-NorOCCl), 1-bicyclo[2.2.2]octyloxychlorocarbene (1-BcoOCCl), and 1-adamantyloxychlorocarbene (1-AdOCCl) were generated in dichloroethane (DCE) by photolysis of the appropriate diazirines. The exclusive product in each case was the bridgehead alkyl chloride formed by fragmentation of the carbene to [R+ OC Cl-] ion pairs, loss of CO, and cation-anion collapse. In mixtures of methanol and DCE, each carbene gave three products: RCl, ROH, and ROMe. RCl and ROMe resulted from competition between ion pair collapse and methanol capture of the cation. ROH resulted from methanol capture of the carbene (before fragmentation), followed by eventual methanolysis and hydrolysis of ROCH(Cl)OMe. The ratios of carbene capture to carbene fragmentation fell in the order 1-NorOCCl > BcoOCCl > 1-AdOCCl; 1-Nor+ was the least stable cation and the slowest to form by fragmentation, so that this carbene was the most readily captured. This trend was accentuated in methanol-pentane mixtures, where ionic fragmentation was further slowed in the less polar solvent. Laser flash photolysis with either UV or time-resolved infrared (TRIR) monitoring permitted the determination of the absolute rate constants for fragmentations of the carbenes in DCE at 25 °C. The rate constants (s-1) were: 1-NorOCCl (3.3 × 104), 1-BcoOCCl (1.5 × 105), and 1-AdOCCl (5.9 × 105). The rate constants decreased in the order of increasing strain in the resulting bridgehead carbocation, but the range of rate constants was compressed to a factor of only ～18. This constrasts with the factor of 1010 by which the acetolysis of 1-AdOTs at 70 °C exceeded that of 1-NorOTs. The fragmentation of 1-NorOCCl to the ion pair was 3 × 1015 times faster than the acetolysis of 1-NorOTs. The activation energies were measured as 9.0 kcal/mol (log A = 11.2 s-1) for the fragmentation of 1-NorOCCl and 4.4 kcal/mol (log A = 8.44 s-1) for that of 1-BcoOCCl both in DCE. B3LYP/6-31G* computed activation energies in simulated DCE were 14.6 and 2.7 kcal/mol, respectively. Copyright
Interpretation of the Reactivity of Benzyl Free Radical towards Peroxyacids in Terms of Orbital Interactions. Competition between Energy Gap Control and Overlap Control
Fossey, Jacques,Lefort, Daniel,Massoudi, Massoud,Nedelec, Jean-Yves,Sorba, Jeanine
, p. 781 - 786 (2007/10/02)
The factors which control the reactivity of alkyl free radicals R. in reaction (i) are studied.The reactivity of R. in (i) depends on the key orbital interaction between the SOMO of the radical and the LUMO of the peroxyacid.This interaction involves two contributions: (i) the energy gap SOMO-LUMO and (ii) the overlap SOMO-LUMO.In reaction (i) the main factor is overlap control which depends on spin delocalisation in the radical R..This proves that reaction (i) does not involve electron transfer.The energy gap control, which depends on the nucleophilic character of R., is only observed when the first factor is constant along a series of R..
N-Nitroso- and N-Nitrotrialkylureas and Their Decomposition
White, Emil H.,Ryan, Thomas J.,Hahn, Bo Sup,Erickson, Ronald H.
, p. 4860 - 4866 (2007/10/02)
The synthesis and decomposition of N-(n-butyl)-N',N'-dimethyl-N-nitrosourea (2a), N-(n-butyl)-N',N'-dimethyl-N-nitrourea (3a), N',N'-dimethyl N-(1-norbornyl)-N-nitrosourea (2b), N',N'-dimethyl-N-(1-norbornyl)-N-nitrourea (3b) are described.Several of the compounds show complex NMR spectra ascribable to rotational isomerism.Decomposition of 2a and 3a gave n-butyl N,N-dimethylcarbamate and tetramethylurea, while decompostion of 2b and 3b in methylene chloride gave 1-norbornyl N,N-dimethylcarbamate and 1-norbornyl chloride.These products are formed via diazotic acid derivatives and carbonium ion pairs; the reaction mechanism is essentially the same as that established for the closely related N-nitrosoamides.In concentrated solutions, nitrosourea 2a yielded a new product, amino acid 20.
