Respondent

Anischenko Viktor Mykolajyvych

Theme

Inverse phase-transfer catalysis and reagents structure in reaction between phosphoryl chloride and phenols

Defence Date

14.06.2017

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.

Dissertation File

Autosummary File