Off-campus UMass Amherst users: To download dissertations, please use the following link to log into our proxy server with your UMass Amherst user name and password.
Non-UMass Amherst users, please click the view more button below to purchase a copy of this dissertation from Proquest.
(Some titles may also be available free of charge in our Open Access Dissertation Collection, so please check there first.)
Generation and trapping of low-coordinate phosphoryl species
Abstract
The low-coordinate phosphoryl species studied in this Dissertation include optically inactive and active metaphosphates, phenyl metaphosphonic anhydride and an optically active O-alkyl metathiophosphate. All of them were generated by the thermal or photochemical fragmentation of the 2,3-oxaphosphabicyclo(2.2.2) -octene 3-oxide(or sulfide) ring system. This system is synthesized by O-insertion with peracids into a C-P bond of 7-phosphanorbornene derivatives with a variety of P-substituents. The short-lived tricoordiante phosphoryl species were confirmed by their trapping reaction products, since they are too reactive to be detected directly. The preferred trapping reagents are alcohols and amino compounds. The electrophilic substitution of hydrogen on a pyyrole ring carbon is also a useful trapping reaction. The low-coordinate phosphoryl species were trapped successfully by these trapping agents and show promise for being good agents of phosphorylation or phosphonylation. The conditions of the generation and trapping of 3-coordinate phosphoryl species are mild and the trapping reactions could be carried out only under homogenous but also heterogenous conditions. The most significant example is the phosphorylation of the surface of silica gel with the optically inactive or active metaphosphates. This provides a potentially useful stationary phase in HPLC, which could be utilized for the separation of basic organic compounds. This indicated that metaphosphate or other highly reactive low-coordinate phosphorus species could be applied to the preparation of a novel type of surface-functionalized silica gel, and other hydroxy-bearing surface, creating unusual surfaces with special characteristics.
Subject Area
Organic chemistry|Biochemistry
Recommended Citation
Wu, Xiao-Ping, "Generation and trapping of low-coordinate phosphoryl species" (1991). Doctoral Dissertations Available from Proquest. AAI9120957.
https://scholarworks.umass.edu/dissertations/AAI9120957