18313-42-3Relevant articles and documents
Reluctant Azoalkanes: The Photochemical Behavior of Acyclic, Bridgehead-Centered Azoalkanes on 185- and 350-nm Irradiation
Adam, Waldemar,Mazenod, Francois,Nishizawa, Yoshinori,Engel, Paul S.,Baughman, Sharon A.,et al.
, p. 6141 - 6145 (1983)
Azo-1-adamantane (1a), azobicyclooctanes (1b and 1c), and azo-1-norbornane (1d) isomerize to cis-azoalkanes but are reluctant to lose nitrogen directly upon long-wavelength irradiation.Use of 185-nm light is shown to enhance deazatization quantum yields considerably, though photoisomerization remains an important reaction.In the case of 1a especially, thermolysis of the cis isomer is the dominant decomposition mechanism at long and probably at short wavelength; however, the cis isomer of 1d is thermally stable.It follows that the second excited singlet state is responsible for deazatization of 1d.The products of photolyisis in pentane have been identified, and the amount of bridgehead radical hydrogen abstraction relative to recombination is found to increase under short-wavelength irradiation.
Electrolytic Reduction of 1,4-Dihalonorbornanes at Mercury Electrodes in Dimethylformamide. Evidence for Propellane as an Intermediate
Carroll, William F.,Peters, Dennis G.
, p. 4127 - 4134 (2007/10/02)
Low-temperature (-34 deg C) electrolytic reduction of 1,4-dibromonorbornane at mercury cathodes in dimethylformamide containing tetraalkylammonium perchlorates yields norbornane, bis(1-norbornyl)mercury, and 1,1'-binorbornyl; reduction of 1,4-diiodonorbornane results in the same three products along with 1-iodonorbornane and other minor species.At potentials for which the mass balance is 100percent, norbornane and bis(1-norbornyl)mercury account for 98percent of the electrolysis products and the coulometric n value is precisely three.When tetramethylammonium perchlorate is utilized as the supporting electrolyte at -34 deg C, there is a range of potentials over which a pronounced polarographic current minimun appears; this low-temperature minimum is attributed to adsorbtion upon the electrode of complex species consisting of tetramethylammonium cations and halide ions.Three key observations suggest that propellane is an intermediate in the electrochemical reduction of the 1,4-dihalonorbornanes: (1) norbornane is derived from 1,4-dihalonorbornane via a three-electron process which does not involve 1-halonorbornane as intermediate; (2) bis(1-norbornyl)mercury is produced by electrolytic reduction of 1,4-dihalonorbornane but not by reduction of 1-halonorbornane; and (3) a species apparently obtained by two-electron reduction of 1,4-dihalonorbornanes is capable of undergoing oligomerization.A polarographic wave seemingly attributable to reduction of propellane is observed.
