Phosphorus–nitrogen compounds: part 63. Mono- and bis-vanillinatobisferrocenyldispiro(N/N)cyclotriphosphazenes and their macrocyclic Schiff-bases: synthesis, structural characterization and isomerism†
Abstract
In this study, mono- and bis-vanillinato-ferrocenyldispirophosphazenes and their Schiff-bases were obtained to investigate the optical and structural properties of cyclotriphosphazenes with stereogenic P-atoms. Accordingly, substitution reactions of two equimolar amounts of the potassium salt of 4-hydroxy-3-methoxybenzaldehyde (potassium vanillinate; KOAr) with one equimolar dichloro trans- (1 and 2) and cis-ferrocenyldispirocyclotriphosphazenes (3 and 4) yielded bis-vanillinato trans- (5 and 6) and cis-dispirocyclotriphosphazenes (8 and 9), respectively. In contrast, using equimolar amounts of trans- (2) and cis-dispirocyclotriphosphazenes (4) with an equimolar amount of KOAr produced the corresponding mono-vanillinato ferrocenyldispirocyclotriphosphazenes, 7 and 10. In addition, condensation reactions of bis-vanillinato trans/cis-dispirophosphazenes (5, 6, 8 and 9) and 1,4-diaminobutane gave rise to novel macrocyclic phosphazene Schiff bases, 11, 12, 13 and 14. The characterization of macrocyclic Schiff bases via1H, 13C and 31P NMR spectroscopy showed that they were present in solution as a mixture of ZZ (syn–syn), ZE (syn–anti) and EE (anti–anti) isomers. The molecular and crystal structures of bis-vanillinato trans- (6) and cis- (9), and mono-vanillinato cis-dispirophosphazenes (10) were elucidated using the X-ray diffraction technique and their absolute configurations were determined as RR, SR and RS, respectively. All dispirophosphazenes have two stereogenic P-atoms, except 10. In addition to two stereogenic P-atoms, mono-vanillinato phosphazene (10) also has a pseudo-asymmetric P-center. Compound 10 was proven to be chiral using the CSA-added 31P NMR spectrum.