Thermal Decomposition and Mass Spectra of the N-Phenyl-, N,N′-Diphenyl-, and N,N′,N″-Triphenylphosphoric Triamides

• Published in: Bulletin of the Chemical Society of Japan Vol. 69; no. 2; pp. 367 - 377
• Main Authors: Fukushima, Kazuhiko, Kanayama, Atsushi, Matsumoto, Yoshihiro, Ono, Shin, Yoshimura, Toshiaki, Morita, Hiroyuki, Tsukurimichi, Eiichi, Shimasaki, Choichiro
• Format: Journal Article
• Language: English
• Published: Tokyo The Chemical Society of Japan 01.02.1996; Chemical Society of Japan
• ISSN: 0009-2673; 1348-0634
• DOI: 10.1246/bcsj.69.367

The thermal decomposition and mass spectra of the N-phenyl- (1), N,N′-diphenyl- (2), and N,N′,N′-triphenylphosphoric triamides (3) were investigated. DTA-TG/DTG, TG-TRAP-GC/MS measurements, IR spectroscopic analyses, mass spectrometric analyses, HPLC analyses, and a kinetic study were carried out to investigate the thermal decomposition. From the analytical results, it was suggested that 1 decomposed while liberating ammonia and aniline, and condensed in several stages; its thermal products at about 160 °C contained 2. Compound 2 decomposed and condensed to form some condensed products at about 200 °C; its thermal products also contained 3. Compound 3 decomposed while liberating aniline to form a cyclic dimer, while the existence of other thermal products was also observed; the cyclic dimer further pyrolyzed in several stages, and 1 and 2 formed a similar condensed product in the 400 to 500 °C temperature range, though that for 3 was different. In addition, the apparent activation energy of the thermal decomposition was estimated and the thermal decomposition process was investigated based on this variation. In the mass spectra using electron impact, 1, 2, and 3 were cleaved along with an elimination of ammonia and/or aniline to form a three-coordinate phosphenimidic amide.