16390-98-0Relevant academic research and scientific papers
Water determines the products: An unexpected Br?nsted acid-catalyzed PO-R cleavage of P(iii) esters selectively producing P(O)-H and P(O)-R compounds
Li, Chunya,Wang, Qi,Zhang, Jian-Qiu,Ye, Jingjing,Xie, Ju,Xu, Qing,Han, Li-Biao
supporting information, p. 2916 - 2922 (2019/06/18)
Water is found able to determine the selectivity of Br?nsted acid-catalyzed C-O cleavage reactions of trialkyl phosphites: with water, the reaction quickly takes place at room temperature to afford quantitative yields of H-phosphonates; without water, the reaction selectively affords alkylphosphonates in high yields, providing a novel halide-free alternative to the famous Michaelis-Arbuzov reaction. This method is general as it can be readily extended to phosphonites and phosphinites and a large scale reaction with much lower loading of the catalyst, enabling a simple, efficient, and practical preparation of the corresponding organophosphorus compounds. Experimental findings in control reactions and substrate extension as well as preliminary theoretical calculation of the possible transition states all suggest that the monomolecular mechanism is preferred.
Bisphosphonate prodrugs. Synthesis and identification of (1-hydroxyethylidene)-1,1-bisphosphonic acid tetraesters by mass spectrometry, NMR spectroscopy and x-ray crystallography
Turhanen, Petri A.,Ahlgren, Markku J.,Jaervinen, Tomi,Vepsaelaeinen, Jouko J.
, p. 115 - 133 (2007/10/03)
The preparation and identification of symmetric, H3CC(OH)[P(O)(OR)2]2, where R=Me, Et, Pr1, Ph, and non-symmetric, H3CC(OH)[P(O)(OR1)(OR2)][P(O)(OR3)(O R4)], where R1=Me, R2=R3=R4=Ph; R1=R2=R3=Ph, R4=Me; R1=R3=Me, R2=R4=Ph; R1=R2=Et, Pr1, Ph and R3=R4=Me: tetraester derivatives of etidronate have been studied. Compounds were prepared from HP(O)(OR1)(OR2) and AcP(O)(OR3)(OR4) species under reflux. Mechanism studies have been made using HP(O)(OCD3)(OPh) and AcP(O)(OMe)(OPh) as starting materials. 1H, 13C, 31P NMR data and the MS fragmentation data in the gas phase are reported. The solid-state structures are given for three of the compounds, where R=Et, Ph and R1=R2=Ph, R3=R4=Me.
