The Studies On The Synthesis And Mass Fragmentation Pathways Of The New-type Pentacoordinate Spirophosphorane Containing Quinolyl Group

The phosphorus compounds are called “the control of the biochemical and physiological reactions” in life system. The DNA 、 RNA hydrolysis process are related to the pentacoordinate phosphorane intermediates or transitin state. The pentacoordinate hydrospirophosphorane is an important kind of pentacoordinate phosphorane compounds. The specialty of hydrospirophosphorane is the P-H bond,which is very active to be precursors for organic synthesis. Most hydrospirophosphoranes contain phosphorous chiral center that exhibit change in the configuration in the chemical reaction processes. Pentaccordiante bis(aminoacyl)spirophosphoranes are very stable in the air and they have three chiral centers, which are very suitable to study the stereochemistry of pentacoordinate phosphorane compounds. Based on the study of pentaccordiante bis(aminoacyl)spirophosphoranes, our group have investigated their Atherton-Todd-type reaction deeply.In this thesis, the Atherton-Todd-type reaction was studied between bis(aminoacyl)spirophosphoranes and 8-hydroxyquinolines, and all products were separated by silica gel column chromatography. The structures of the products were confirmed by NMR 、 HR-MS 、 IR and X-ray diffraction analysis. Moreover, the31P-NMR tracing experiment testified that the reaction went through an intermediate chlorophosphorane, thus the reaction mechanism for the Atherton-Todd reaction between bis(aminoacyl)spirophosphoranes and 8-hydroxyquinolines was presumed.Furthermore, we studied the fragmentation pathways of the products synthesized from hydrospirophosphoranes and 8-hydroxyquinolines by electrospray ionization multistage mass spectrometry(ESI-MSn). The fragmentation pathways of the[M+Na]+ ion were proposed, which was further testified by HR-MS. Combining with the fragmentation pathways of phenoxy spirophosphoranes, we found that charge distribution may influence the fragmentation pathways and the result was estimated by the B3LYP/6-311+G(d, p) model of Density Fuctional Theory(DFT).The study of fragmentation pathways of these compounds may lay foundation forthe structure analysis of similar compounds by ESI-MSn.In order to study the stereochemical character of pentacoordinate phosphorane compounds, the rotation of N-C(=O) bond of spirophosphorane carbamates was studied. The investigation of the rotation of the N-C(=O) bond of spirophosphorane carbamates was carried out by dynamic 1H NMR, 31 P NMR and theoretical calculations. In addition, the Gibbs free activation, ?G≠, was calculated by Eyring equation and the results were about 16-18 kcal/mol. The DFT method and X-ray diffraction analysis were used to study the preferred conformations of the spirophosphorane carbamates.