2062-48-8Relevant academic research and scientific papers
PHOSPHORORGANISCHE VERBINDUNGEN 96. DIE SELECTIVE VERKNUEPFUNG BIOLOGISCH WICHTIGER FUNKTIONELLER GRUPPEN MIT PHOSPHORORGANISCHEN SAEUREN
Horner, L,Gehring, R.
, p. 157 - 176 (2007/10/02)
Derivatives of phosphinic, phosphonic, and phosphoric acids of the general type R1R2P(O)X show selectivity in their reactions with nucleophiles RYH (R = n-C4H9; Y = O, NR or S) according the Eq. (1); the selectivity depends on the nature of the leaving group (X = Cl, F, CN, N3 or OC6H4NO2(p)) and the base used.The nature of the ligands R1 and R2, exert a comparatively minor influence on the reaction.Method: (a) The phosphylating agent R1R2P(O)X was allowed to react with mixture of two nucleophiles RYH and RY'H in competition (Reagent ratio 1:1:1).The product mixture (R1R2P(O)YR + R1R2P(O)Y'R was then analyzed. (b) Compounds of the type HY-CH2-CH2-Y'H (serine-n-butylamide L-cysteinmethylester) were reacted with the phosphylating agent R1R2P(O)X (reagent ratio 1:1) according the Eqs. (3) and (4) respectively.The products were isolated, identified and the yields quantitatively determined.Results: For X = F, CN, OC6H4NO2 (p), the O-ester is formed virtually exclusively.For X = Cl, only amides are formed.Azides (X = N3) show no selectivity.In competition reactions using n-butylamine and n-butylthiol, the organophosphorus chlorides (X = Cl) were found to be N-selective,, whereas the corresponding cyanides (X = CN) were S-selective.In competition reactions using n-butanol and n-butylthiol, the organophosphorus fluorides (X = F) p-nitrophenylesters (X = OC6H4NO2(p)) and cyanides (X = CN) were all O-selective.
PHOSPHORORGANISCHE VERBINDUNGEN 95. Beschleunigte Hydrolyse von Organophosphorverbindungen durch Phasentransferkatalyse und H2O2 als Supernucleophil
Horner, Leopold,Kappa, H. Wilfried
, p. 339 - 348 (2007/10/02)
The alkaline hydrolyses of the physiologically active phosphor compounds: butyl-phenylfluorophosphonate 1 and di-isopropyl-fluorophosphate were studied under phase-transfer (PT) conditions.The influence of pH, the structure of the phase-transfer catalyst, the nature of the organic phase and the use of the supernucleophile HO2- on the hydrolysis was investigated.The hydrolysis of 1 is accelerated by a factor of ca. 550 (toluene) resp. ca. 520 (tetrachloroethylene) compared with the uncatalysed reaction.In concrete terms, the compound 1 can be completely hydrolysed in three (tuloene) resp. in one minute (tetrachloroethylene) under optimal conditions.
