Phosphorus-nitrogen compounds. spiro- and crypta-phosphazene derivatives: synthesis and spectral investigations. Structure of butane- N, N'-bis(1,4-oxybenzyl)- spiro(propane-1,3-diamino)tetrachlorocyclo-2λ 5, 4λ 5, 6λ 5-triphosphazatriene. Part VII

Abstract

The condensation reactions between trimer, N3P3Cl6, and diamines, 2 and 4 and {1-{N-[1-(2-hydroxynaphthylmethyl)aminomethylidene]}-2(1H)-naphthalenone, 3, yielded the new spiro-cyclic- (5 and 8) and the novel spiro-phosphazene (7) derivatives, respectively. The fully substituted phosphazene (6) was also obtained from the reaction of 5 with the excess of pyrrolidine. Compounds (4-8) have been characterized by elemental analyses, FTIR, H-1-, C-13-, P-31-NMR, HETCOR, COSY and MS. The structure of crypta-phosphazene, 8, has been examined crystallographically. Compound 8 is the first example of the crypta-phosphazene derivatives. The P-31-NMR spectra of compounds 7 and 8 indicate that, both of the compounds have anisochronism because of the stereogenic centers. The pyramidal geometry of two spiro-cyclic nitrogen atoms in compound 8, gives rise to stereogenic property. The sums of the bond angles around N-4 and N-5 nitrogens are 350.6(2) and 349.6(3)degrees, respectively. Compound 8 crystallizes in the triclinic space group P (1) over bar with a = 8.798(3), b = 10.498(3) and c = 15.689(4) Angstrom; alpha = 91.35(2), beta = 103.39(4) and gamma = 102.88(4)degrees; V = 1369.9(7) Angstrom(3), Z = 2 and D-x = 1.491 g cm(-3). It consists of a non-centrosymmetric, non-planar phosphazene ring with a bulky dibenzo-diazacrown etheric side group. (C) 2004 Elsevier B.V. All rights reserved.