Phosphorus-nitrogen compounds. Part 20: Fully substituted spiro-cyclotriphosphazenic lariat (PNP-pivot) ether derivatives.

The condensation reactions of partly substituted spiro-cyclotriphosphazenic lariat (PNP-pivot) ethers, N(3)P(3)[(o-NHPhO)(2)R]Cl(4) [where R=-CH(2)CH(2)- (1) and -CH(2)CH(2)OCH(2)CH(2)- (2)] with morpholine and 1,4-dioxa-8-azaspiro[4,5]decane (DASD) produce fully substituted morpholino (3 and 4) and 1,4-dioxa-8-azaspiro[4,5]deca (5 and 6) phosphazenes. These are the new examples of the spiro-cyclophosphazenic lariat ether derivatives with N(2)O(x) (x=2 and 3) donor type containing 11- and 14-membered macrocycles. The solid state structures of 3, 5 and 6 have been determined by X-ray diffraction techniques. Compound 3 has intermolecular N-H...O hydrogen bond, compound 5 has intra- and intermolecular N-H...O hydrogen bonds, while compound 6 has intramolecular N-H...O and O-H...N and intermolecular N-H...O and O-H...O hydrogen bonds. The correlations of the endocyclic (alpha) and exocyclic (alpha') NPN bond angles with deltaP(spiro) values are investigated. The structural investigations of 3-6 have been verified by elemental analyses, MS, FTIR, (1)H, (13)C and (31)P NMR, DEPT and HETCOR techniques. Copyright 2010 Elsevier B.V. All rights reserved.