REACTIONS OF NITRO AND NITROSO COMPOUNDS WITH DIFLUORAMINE

Nitro and nitroso compounds were used as alkylating agents for difluoramine in the presence of strong acid. 1,1-Dibromo-1-nitrobutane, 1,1-dichloro-1-nitrobutane, 1-bromo-1-fluoro-1-nitropropane, and α, α0-dibromo-α-nitrotoluene gave 1,1-dibromo-1-(difluoramino)butane, 1,1-dichloro-1-(difluoramino)butane, 1-bromo-1-difluoramino-1-fluoropropane, and α,α-dibromo-α-(difluoramino)toluene, respectively. Prolonged reactions converted the dibromo derivatives into 1-bromo-1,1-bis(difluoramino) compounds. 2-Halo-2,4,4-trinitropentane gave 3,5-dimethylisoxazole and 2,2,4,4-tetrakis(difluoramino)pentane, rationalized by a mechanism involving intramolecular nitro 0 alkylation. 1-Chloro-1-nitrosocyclohexane and 1-nitro-1-nitrosocyclohexane gave 1,1-bis(difluoramino)cyclohexane with fuming sulfuric acid but, with BF3• H3PO4 as catalyst, 1-nitro-1-nitrosocyclohexane gave nitrocyclohexane and 1-nitrocyclohexyl-Nʹ-fluorodiimide N-oxide. The latter was shown not to be an intermediate in the sulfuric acid catalyzed reaction. Unstable nitroso derivatives were prepared from 1-chloro-1-nitroalkanes, which reacted with difluoramine and fuming sulfuric acid to give 1-chloro-1,1-bis(difluoramino)alkanes. Alkyl nitrites acted as nitrosation agents toward difluoramine. © 1969, American Chemical Society. All rights reserved.