80358-47-0Relevant 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 97. Die Diphenylphosphinyl- und die Diphenylthiophosphinylgruppe als selektive Schutzgruppe fuer die Mercaptofunktion. Nucleophile Abloesung der Thioloestergruppe aus Thiophosphin-, Thiophosphon- und Thiophosphorsaeure-S-estern durch nicht solvatisierte...
Horner, L.,Gehring, R.,Lindel, H.
, p. 349 - 356 (2007/10/02)
Diphenylphosphinic acid cyanide and diphenylthiophosphonic acid cyanide react selectively with the mercaptogroup even in presence of primary aminogroups.The thioloesterbond in thiophosphinic, thiophosphonic and thiophosphoric acid S-esters is cleaved under mild conditions by unsolvated fluoride ions F*3H2O (R = C4H9) and CsF> in methylene chloride, chloroform or THF. (C6H5)2P(O)CN and (C6H5)2P(S)CN are therefore protecting group reagents for mercaptans.Diphenylphosphinic acid chloride and diphenylthiophosphinic acid chloride are N-selective in competing reactions using butylamine/butylmercaptan.In contrast to the corresponding S-selective cyanides no selectivity is observed using cysteamine and cysteinmethylester.
