Karl E. Swenson

Dimethylpyrrolidinium amalgam formation and catalysis of organic electroreductions

Abstract The cathodic reduction of several tetraalkylanunonium cations on mercury in DMF with 0.1 M tetrabutylainmonium fluoroborate as the supporting electrolyte was investigated and dimethylpyrrolidinium (DMP + ) was chosen as a representative for an intensive study. It was shown that DMP + reacts by a reversible one-electron process forming an insoluble material best described as an amalgam. The material has a half life of 6.3 h at 5°C and consequently reacts with the solvent, yielding dimethylamine and regenerating DMP + . It was also shown that DMP + is a catalyst for the reduction of cyclohexanone. The catalytic nature of the DMP + reactions with DMF and cyclohexanone and the possible involvement of reduced tetraalkylammonium intermediates in other organic electroreductions are discussed.

The rearrangement of 4,4-diphenylcyclohexa-2,5-dienylidene

Abstract Pyrolytic decomposition of the Li salt of the tosylhydrazone of 4,4-diphenyl-2,5-cyclohexadienone produces a mixture of biphenyl, o -terphenyl, p -terphenyl, methyl- o -terphenyl and the azine of 4,4-diphenyl-2,5-cyclohexadienone ( 13 ). Insight into the reaction pathway was provided by the pyrolytic decomposition of 2-deuterio tosylhydrazone 8a which generates o -terphenyl 10a and 10b in ratio of 69:31. These results are interpreted in terms of the carbene rearrangements of Schemes 2, 3 and 5.