1571-33-1Relevant articles and documents
Two step acidic hydrolysis of dialkyl arylphosphonates
Harsági, Nikoletta,Rádai, Zita,Kiss, Nóra Zsuzsa,Szigetvári, Aron,Keglevich, Gy?rgy
, p. 38 - 39 (2020)
The HCl-catalyzed hydrolysis of dialkyl arylphosphonates monitored by 31P NMR spectroscopy has revealed two consecutive steps characterized by pseudo first order rate constants k1 and k2. A reactivity order for the two steps and for the overall two step hydrolysis has been derived depending on the alkoxy and aryl substituents. Besides the AAc2 mechanism, the AAl1 route has been substantiated for the PriO substituent.
Inhibition of serine β-lactamases by acyl phosph(on)ates: A new source of inert acyl [and phosphyl] enzymes
Li, Naixin,Pratt
, p. 4264 - 4268 (1998)
Acyl phosph(on)ates are shown to inhibit serine β-lactamases and provide a new source of relatively stable complexes. Thus, benzoyl phenyl phosphate, benzoyl phenylphosphonate, and dibenzoyl phosphate react with the class C β-lactamase of Enterobacter cloacae P99 at micromolar concentrations to form an acyl enzyme of half-life about 40 s. The phosphonate reacts further more slowly to produce a much more inert complex. Dibenzoyl phosphate reacts with the class A TEM β-lactamase to from an acyl enzyme of half-life about 8 s and, more slowly, reaching completion after an average of about 80 turnovers, a more inert complex, of half-life about 2 h. The acyl phosphonates thus represent a new starting point for the design of β- lactamase inhibitors and perhaps of antibacterial agents.
Kinetics and mechanism of the oxidation of lower oxyacids of phosphorus by hexamethylenetetramine bromine
Mehla, Satish K.,Kothari, Seema,Banerji, Kalyan K.
, p. 165 - 170 (2000)
The oxidation of lower oxyacids of phosphorus by hexamethylenetetramine bromine (HABR) in glacial acetic acid resulted in the formation of corresponding oxyacids with phosphorus in a higher oxidation state. The reaction exhibited 2:1 stoichiometry. The reaction is first order with respect to HABR. Michaelis-Menten-type kinetics were observed with respect to the acids. The formation constant of the phenylphosphinic acid-HABR complex also has been determined spectrophotometrically. The thermodynamic parameters for the complex formation and the activation parameters for their decomposition were calculated. The reaction showed the presence of a substantial kinetic isotope effect. It is proposed that the HABR itself is the reactive oxidizing species. It has been shown that the pentacoordinated tautomer of the phosphorus oxyacid is the reactive reductant. A suitable mechanism has been proposed.
C-P bond formation of cyclophanyl-, and aryl halides: Via a UV-induced photo Arbuzov reaction: A versatile portal to phosphonate-grafted scaffolds
Br?se, Stefan,Hassan, Zahid,Nieger, Martin,O?wald, Simon,Zippel, Christoph
, p. 3309 - 3312 (2022/02/11)
A new versatile method for the C-P bond formation of (hetero)aryl halides with trimethyl phosphite via a UV-induced photo-Arbuzov reaction, accessing diverse phosphonate-grafted arenes, heteroarenes and co-facially stacked cyclophanes under mild reaction
Hydrolysis and alcoholysis of phosphinates and phosphonates
Harsági, Nikoletta,Keglevich, Gy?rgy,Sz?ll?si, Betti,Varga, Petra Regina
, (2021/11/04)
Phosphinic and phosphonic acids useful intermediates and biologically active compounds may be prepared from their esters: phosphinates and phosphonates, respectively, by acid-catalyzed hydrolysis either on conventional heating or on MW irradiation. The transesterification of alkyl phosphinates took place only in the presence of suitable ionic liquids as the catalysts. In the cases of phenylphosphonates, depending on the nature of the ionic liquid, the formation of the ester was accompanied by the fission of the C–O bond.
Hydrolysis-Based Small-Molecule Hydrogen Selenide (H2Se) Donors for Intracellular H2Se Delivery
Bolton, Sarah G.,Chouinard, Julie E.,Garcia, Arman C.,Golledge, Stephen L.,Newton, Turner D.,Pluth, Michael D.,Zakharov, Lev N.
, p. 19542 - 19550 (2021/11/23)
Hydrogen selenide (H2Se) is a central metabolite in the biological processing of selenium for incorporation into selenoproteins, which play crucial antioxidant roles in biological systems. Despite being integral to proper physiological function, this reactive selenium species (RSeS) has received limited attention. We recently reported an early example of a H2Se donor (TDN1042) that exhibited slow, sustained release through hydrolysis. Here we expand that technology based on the P-Se motif to develop cyclic-PSe compounds with increased rates of hydrolysis and function through well-defined mechanisms as monitored by 31P and 77Se NMR spectroscopy. In addition, we report a colorimetric method based on the reaction of H2Se with NBD-Cl to generate NBD-SeH (λmax = 551 nm), which can be used to detect free H2Se. Furthermore, we use TOF-SIMS (time of flight secondary ion mass spectroscopy) to demonstrate that these H2Se donors are cell permeable and use this technique for spatial mapping of the intracellular Se content after H2Se delivery. Moreover, these H2Se donors reduce endogenous intracellular reactive oxygen species (ROS) levels. Taken together, this work expands the toolbox of H2Se donor technology and sets the stage for future work focused on the biological activity and beneficial applications of H2Se and related bioinorganic RSeS.
Wet and dry processes for the selective transformation of phosphonates to phosphonic acids catalyzed by br?nsted acids
Li, Chunya,Saga, Yuta,Onozawa, Shun-Ya,Kobayashi, Shu,Sato, Kazuhiko,Fukaya, Norihisa,Han, Li-Biao
, p. 14411 - 14419 (2020/12/29)
A "wet"process and two "dry"processes for converting phosphonate esters to phosphonic acids catalyzed by a Bronsted acid have been developed. Thus, in the presence of water, a range of alkyl-, alkenyl-, and aryl-substituted phosphonates can be generally hydrolyzed to the corresponding phosphonic acids in good yields catalyzed by trifluoromethyl sulfonic acid (TfOH) at 140 °C (the wet process). On the other hand, with specific substituents of the phosphonate esters, the conversion to the corresponding phosphonic acids can be achieved under milder conditions in the absence of water (the dry process). Thus, the conversion of dibenzyl phosphonates to the corresponding phosphonic acids took place smoothly at 80 °C in toluene or benzene in high yields. Moreover, selective conversion of benzyl phosphonates RP(O)(OR′)(OBn) to the corresponding mono phosphonic acids RP(O)(OR′)(OH) can also be achieved under the reaction conditions. The dealkylation via the generation of isobutene of ditert- butyl phosphonate, and the related catalysis by TfOH took place even at room temperature to give the corresponding phosphonic acids in good to high yields. Nafion also shows high catalytic activity for these reactions. By using Nafion as the catalyst, phosphonic acids could be easily prepared on a large scale via a simple process.
METHOD FOR PRODUCING PHOSPHONIC ACID DERIVATIVE
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Paragraph 0045-0047; 0052, (2020/10/27)
PROBLEM TO BE SOLVED: To provide a method for producing a phosphonic acid derivative, in which the reaction proceeds under relatively mild reaction conditions without using hydrogen halide or a metal catalyst. SOLUTION: Provided is a method for producing a phosphonic acid derivative represented by formula (1), comprising a step in which an ester group-containing phosphonic acid derivative is reacted in a solvent or without a solvent in the presence of a superacid catalyst. (In formula (1), R1 and R2 are each independently a substituted or unsubstituted hydrocarbon group that may contain a heteroatom, n is a natural number of 1 to 3, m is a natural number of 0 to 2, o is a natural number of 0 to 1, and n + m + o = 3.). SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
Discovery of New H2S Releasing Phosphordithioates and 2,3-Dihydro-2-phenyl-2-sulfanylenebenzo[d][1,3,2]oxazaphospholes with Improved Antiproliferative Activity
Feng, Wei,Teo, Xin-Yi,Novera, Wisna,Ramanujulu, Pondy Murugappan,Liang, Dong,Huang, Dejian,Moore, Philip K.,Deng, Lih-Wen,Dymock, Brian W.
supporting information, p. 6456 - 6480 (2015/09/07)
Hydrogen sulfide (H2S) is now recognized as a physiologically important gasotransmitter. Compounds which release H2S slowly are sought after for their potential in therapy. Herein the synthesis of a series of phosphordithioates based on 1 (GYY4137) are described. Their H2S release profiles are characterized using 2,6-dansyl azide (2), an H2S specific fluorescent probe. Most compounds have anticancer activity in several solid tumor cell lines and are less toxic in a normal human lung fibroblast, WI38. A preferred compound, 14, with 10-fold greater anticancer activity than 1, was shown to release H2S in MCF7 cells using a cell active probe, 21. Both permeability and intracellular pH (pHi) were found to be significantly improved for 14 compared to 1. Furthermore, 14 was also negative in the AMES test for genotoxicity. Cyclization of these initial structures gave a series of 2,3-dihydro-2-phenyl-2-sulfanylenebenzo[d][1,3,2]oxazaphospholes, of which the simplest member, compound 22 (FW1256), was significantly more potent in cells. The improved therapeutic window of 22 in WI38 cells was compared with three other cell types. Potency of 22 was superior to 1 in MCF7 tumor spheroids and the mechanism of cell death was shown to be via apoptosis with an increase in cleaved PARP and activated caspase-7. Evidence of H2S release in cells is also presented. This work provides a "toolbox" of slow-release H2S donors useful for studies of H2S in biology and as potential therapeutics in cancer, inflammation, and cardiovascular disease. (Chemical Equation Presented).
Phosphonothioate hydrolysis by molybdocene dichlorides: Importance of metal interaction with the sulfur of the thiolate leaving group
Kuo, Louis Y.,Baker, Devon C.,Dortignacq, Adria K.,Dill, Kristina M.
, p. 4759 - 4765 (2013/09/24)
The metallocene bis(cyclopentadienyl)molybdenum(IV) dichloride Cp 2MoCl2 hydrolyzes O,S-diethyl phenylphosphonothioate (1) with only P-S scission to yield a phosphonate under mild aqueous conditions. In terms of degrading phosphonoth
