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Hydrolytic instability of C-F bonds in 2,2,2-trifluoroethyl-phosphinic acid
systems: formation of carboxymethylphosphinic acid derivatives
#MMPMID41384054
Koucký F
; Císa?ová I
; Kotek J
RSC Adv
2025[Dec]; 15
(57
): 49109-49118
PMID41384054
show ga
The trifluoromethyl group in 2,2,2-trifluoroethylphosphonic acid remains stable
against hydrolysis. However, in contrast, 2,2,2-trifluoroethylphosphinic acid and
its derivatives display unexpectedly low hydrolytic stability of the C-F bond in
alkaline solutions. When treated with bases such as alkali metal hydroxides or
tetramethylammonium hydroxide, these compounds undergo hydrolysis of the R-CF(3)
group, producing R-COO(-) and F(-) quantitatively. This phenomenon is easily
observed using (19)F NMR spectroscopy, which provides a clear analytical
signature of the transformations. Although the resulting carboxymethylphosphinic
acid derivatives somewhat resemble malonic or phosphonoacetic acid derivatives,
they demonstrate remarkable stability in both strong acidic and alkaline
solutions, where decarboxylation analogous to the malonic ester synthesis or
dephosphorylation similar to the Horner-Wadsworth-Emmons reaction would be
expected. The observed hydrolytic instability of the
2,2,2-trifluoroethylphosphinic acid fragment brings the possibility to introduce
a bifunctional carboxymethylphosphinic acid chelating group(s) in, e.g.,
chelators used in radiomedicine.
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