Respondent
Theme
Inverse phase-transfer catalysis and reagents structure in reaction between phosphoryl chloride and phenols
Defence Date
Annotation
Inverse phase-transfer catalysis (IPTC) was used to perform reaction between
reagents in two-phase medium water/dichloromethane. (N-diphenoxyphosphoryloxy)-4-
dimethylaminopyridinium chloride, perchlorate and tetraphenylborate were synthesized to
confirm that reaction paths through ionic intermediate. Structure of synthesized salts were
confirmed with IR and NMR spectroscopy
The extended scheme of process that includes formation of tetraphenyl
pyrophosphate was proposed based on the collected experimental data. Reaction rate
constants of interaction between pyridine N-oxides and diphenyl phosphoryl chloride for 20
different temperatures were determined using equations based on proposed scheme. It was
found that the process of phosphorylation at 5 °C using dimethylaminopyridine N-oxide
possible to achieve almost quantitative yield the desired product. According to the
simulation of reaction between diphenyl phosphoryl chloride and pyridine-N-oxides
transition state have geometry of triangular bipyramid and Gibbs free energy of activation
essentially depends on the conformation of diphenyl phosphoryl chloride.
Several phosphates were synthesized with using IPTC method and optimal reaction
condition. The structure of the synthesized compounds was confirmed by IR and NMR
spectroscopes’. The influence of spatial arrangement of substituent on vibrational
frequencies and shielding of 31P were determined by analysis of the calculated IR and
NMR spectra.