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, N 3P 3Cl 6, 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, 1H-, 13C-, 31P-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 31P-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)°, respectively. Compound 8 crystallizes in the triclinic space group P 1 with a=8.798(3), b=10.498(3) and c=15.689(4) Å; α=91.35(2), β=103.39(4) and γ=102.88(4)°; V=1369.9(7) Å 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.