Synthesis and Chemistry of Polynitroalkanes and Polynitroolefins

摘要

The objective of the current study was to develop new methods for carbon, nitroxides, and nitrogen bond formation. Below we summarize the results of there major research areas: (1) Nonacidic amine nitration. Two new nonacidic nitrating agents were developed that proved to be effective in secondary nitramine synthesis; 2,2-bis(chloromethyl)propane-1,3-diol dinitrate and 2-trifluoromethyl-2-propyl nitrate. These two nitrating reagents give nitramines in 60-100% yield without nitrosamine by-product formation. The reaction scope of these new lipophilic nitrophores appears to be limited only by steric crowding of the amine substrate. (2) Nitroacetylene synthesis. A general method was developed and refined for nitroacetylene synthesis by treating substituted bis-trialkylsilyl acetylenes with either nitronium hexafluorophosphate or freshly triturated nitronium tetrafluoroborate in polar solvents such as nitromethane and acetonitrile. Using this procedure, we prepared several new nitroacetylenes in 30-70% yields. Preliminary experiments indicate that the electrophilic nitroacetylenes behave in an anticipated manner toward dienes, 1,3-dipolaraphiles, and general acetylenic addition reactions. (3) Nitrodealumination. We examined the interactions between vinylaluminate salts and various nitrating agents. This effort culminated in nitroolefin preparation by treating vinylaluminum and vinylaluminate salts with tetranitromethane. Using this procedure, we converted several aryl and aliphatic acetylenes to the corresponding nitroolefin in low to moderate yields.