Department of Chemistry, Ankara University, Tandoğan 06100, Ankara, Turkey.
Spectrochim Acta A Mol Biomol Spectrosc. 2010 Aug;76(3-4):401-9. doi: 10.1016/j.saa.2010.04.007. Epub 2010 May 4.
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.
部分取代的螺环环三磷杂氮翁（PNP-枢轴）醚，N(3)P(3)[(o-NHPhO)(2)R]Cl(4) [其中 R=-CH(2)CH(2)-（1）和-CH(2)CH(2)OCH(2)CH(2)-（2）]与吗啉和 1,4-二氧杂-8-氮杂螺[4.5]癸烷（DASD）的缩合反应生成完全取代的吗啉（3 和 4）和 1,4-二氧杂-8-氮杂螺[4.5]癸烷（5 和 6）磷杂环。这些是具有 N(2)O(x)（x=2 和 3）供体类型的螺环环磷杂氮翁醚衍生物的新实例，包含 11 和 14 元大环。通过 X 射线衍射技术确定了 3、5 和 6 的固体结构。化合物 3 具有分子间的 N-H...O 氢键，化合物 5 具有分子内和分子间的 N-H...O 氢键，而化合物 6 具有分子内的 N-H...O 和 O-H...N 以及分子间的 N-H...O 和 O-H...O 氢键。研究了内环（alpha）和外环（alpha'）NPN 键角与 deltaP(spiro) 值的相关性。通过元素分析、MS、FTIR、(1)H、(13)C 和 (31)P NMR、DEPT 和 HETCOR 技术验证了 3-6 的结构研究。
