期刊
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY
卷 44, 期 10, 页码 1451-1463出版社
MAIK NAUKA/INTERPERIODICA/SPRINGER
DOI: 10.1134/S1070428008100096
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资金
- Russian Foundation for Basic Research [07-03-00223, 06-03-32158a]
- Presidium of the Russian Academy of Sciences
- Ministry of Education and Science of the Russian Federation [RNP.-2.2.2.2.5592]
- President of the Russian Federation [NSh-363.2008.3]
Quantum-chemical calculations in terms of the density functional theory showed that cyclopolyenyl isocyanides RNC are considerably less stable than the corresponding cyanides and that they are capable of undergoing RNC -> RCN isomerization according to both 1,2-shift mechanism (cyclopropenyl and cyclopentadienyl isocyanides; Delta E double dagger = 35.0 and 37.5 kcal/mol, respectively) and previously unknown 2,5-sigmatropic shift mechanism (cycloheptatrienyl isocyanide, Delta E double dagger = 26.4 kcal/mol). Migration of cyano group in the cyclopentadiene and cycloheptatriene systems follows the 1,5-sigmatropic shift pattern. The activation barrier to 1,5-shift of cyano group around the cycloheptatriene ring was estimated by dynamic NMR in deuterated nitrobenzene (Delta G double dagger(190C) = 26.5 kcal/mol).
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