Syntheses of Novel Nitrogen and Phosphorus Heterocycles

摘要

1-Dichlorophospha-3,5-perfluoro-n-heptyl (or perfluoroalkylether)-2,4,6-triazines were synthesized by interaction of imidoylamidines with phosphorus pentachloride. In a parallel approach, 1,3-bis(phenylchlorophospha)-5-perfluoroalkyl (or perfluoroalkylether)-2,4,6-triazines were obtained from the reaction of amidines with imido-diphenyl-diphosphinic acid pentachloride. Replacement of chlorine by thiophenyl and azido groups proceeded readily. Di-(phenylchlorophospha)-s-triazine was found to undergo further reaction with amidine in a 1:2 ratio. The existence of stereo-isomerism was indicated. The thiophenyl-substituted phospha-s-triazines functioned as corrosion and oxidation inhibitors in perfluoroalkylether fluids; however, their thermal and thermal oxidative stability was lower than that of the phenyl analogues. Both the mono- and diphospha-s-triazines were completely degraded in 24 hr at 316 C in nitrogen; diphenylsulfide was one of the major products. Mass spectral analysis of the phenyl-free phospha-s-triazines revealed that the specific breakdown patterns are ring specific not phenyl-substituent dependent. Perfluoro-n-octanonitrile was found to react with aniline both in the absence and presence of solvents. Treatment of perfluoro-n-octanonitrile with phenylphosphine gave tetraphenyltetraphosphine and a spectrum of reduction and interaction products of perfluorooctanonitriles, as well as phenylphosphine addition compounds.