Selektivitätsstudien: OH-, NH- und SH-gruppenspezifische Reagentien – ihre Anwendung in der organischen Analytik und als Schutzgruppen in der Synthese†

Abstract

Selectivity: OH-, NH- and SH-Groupspecific Reagents. The Application in Organic Analysis and as Protective Groups Phosphylhalides and -pseudohalides R1R2P(O)X (X = Cl, F, CN, N3, OC6H4NO2(p)) reactdepending on X- with a different selectivity with OHNH- and SH-groups. Vinylsulfones ArSO2CH = CH2 are SH-selective. Silanes R3SiH are OH-selective. By exchange of one ligand bound on P, SO2 or Si by the 5-dimethylamino resp. the 5-methoxynaphthalinogroup reagents are formed, which combine group selectivity with fluorescence. The fluorescence is quenched if a ligand or the leaving group is substituted by a NO2-group. The fluorescence appears again if after the group selective fixation the ligand with the nitrogroup is split off. In serine enzymes (α-chymotrypsine, trypsin, butyryl- and acetylcholinesterase, subtilisine) and insuline (after the reductive opening of the S-S bridges) the primary OH-groups in the active site in the enzymes resp. the SH groups in the reduced insuline were substituted with fluorescing groups using group selective fluorescing reagents.