A New Technique for Generation of 3-Coordinate Phosphoryl Species: Applications in Surface Modification.
Abstract
O-Alkyl N-substituted phosphoramidic acids fragment thermally with the release of an alkyl metaphosphate. Best results are obtained with large N-substituents. The dipolar form is the actual species undergoing fragmentation. When substrates with OH groups (alcohols, phosphorus acids, solids like silica gel or zeolites, cellulose and fabrics) are present in the medium, phosphorylation takes place. The process was extended to include the generation of alkyl metathiophosphates by fragmentation of related phosphoramidothioates, similarly useful in thiophosphorylation. When phenyl replaced O-alkyl (as in phenylphosphonamidic acids), fragmentation occurred to release phenyldioxophosphorane, also useful in phosphorylation of OH species. A new approach in 7-phosphanorbornene chemistry involves synthesis of derivatives with very large P-substituents. These were prepared from phospholes bearing these substituents. The phosphanorbornenes are potential precursors of low-coordination phosphoryl species. Aryl phosphenites were generated by thermolysis of l,3,5,2,4,6-trioxatriphosphorinanes, and their reactivity to OH species studied. The OH species was shown both to add to the P=O group and to displace the OR group.
Document Details
- Document Type
- Technical Report
- Publication Date
- Aug 12, 1996
- Accession Number
- ADA313598
Entities
People
- Louis D. Quin
Organizations
- University of Massachusetts Amherst