The starting compound, tetrachloro-4-fluorobenzyl-spiro(N/O)cyclotriphosphazene (), was synthesized from the substitution reaction of hexachlorocyclotriphosphazatriene (NPCl; trimer; ) with sodium 3-(4-fluorobenzylamino)-1-propanoxide (). Reactions of spiro () with excess 1-(2-aminoethyl)-piperidine, 4-(2-aminoethyl)-morpholine, 1-(2-hydroxyethyl)piperidine and 4-(2-aminoethyl)morpholine yielded the fully substituted cyclotriphosphazene derivatives (), respectively. Elemental analysis, mass spectrometry (ESI-MS), FTIR, H-, C- and P-NMR data confirmed the structure of the new cyclotriphosphazenes (); and the crystal structure of was also identified by X-ray crystallography.
View Article and Find Full Text PDFA great wealth of structural information about phosphazenes can be gleaned from the combined spectroscopic and crystallographic data. When data from P NMR spectroscopy and X-ray crystallography are put together like pieces in a puzzle, a number of correlations can be obtained for phosphazene derivatives. A systematic study concerning the correlations among the structural parameters (e.
View Article and Find Full Text PDFThe results of a systematic study of -cyclotri/tetraphosphazenes with ferrocenyl pendant arm on the basis of correlation between structural parameters were presented. The main parameters were obtained from Xray crystallography and P NMR results in order to investigate the relationship between the δ P shift values and endocyclic and exocyclic NPN bond angles, and electron density transfer parameters. Structural parameters derived from 11 types of the ferrocenyl cyclophosphazene derivatives with 5- to 7-membered -rings introduced to the literature from our research group were studied and compared with each other.
View Article and Find Full Text PDFA number of novel ansa-spiro-ansa (asa) cyclotetraphosphazenes (1a-5b) was prepared in the range of 63-90 % yields. The structures of the compounds were verified by MS, FTIR, (1)H, (13)C{(1)H} and (31)P{(1)H} NMR, heteronuclear single quantum coherence (HSQC), and heteronuclear multiple-bond correlation (HMBC) techniques. The crystal structures of 1b, 2c and 5a were determined by X-ray crystallography.
View Article and Find Full Text PDFThe reactions of octachlorocyclotetraphosphazene, N(4)P(4)Cl(8), with N(2)O(2) donor-type aminopodands (1a, 1b, 1g, and 1h) afforded two kinds of derivatives, namely, spiro-ansa-spiro (sas) (2a, 2b, 2g, and 2h) and ansa-spiro-ansa (asa) (3a and 3b) phosphazenes. The partly substituted sas phosphazenes (2a and 2b) reacted with excess pyrrolidine and morpholine in tetrahydrofuran to produce the tetrapyrrolidino (2c and 2d) and morpholino (2e and 2f) derivatives. The reactions of the asa phosphazenes (3a and 3b) with excess pyrrolidine and morpholine produced gem-2-trans-6-dichloropyrrolidinophosphazenes (3c and 3d) and -morpholinophosphazenes (3e and 3f).
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