598-02-7Relevant articles and documents
Rhodium-catalyzed phosphorylation reaction of water-soluble disulfides using hypodiphosphoric acid tetraalkyl esters in water
Arisawa, Mieko,Fukumoto, Kohei,Yamaguchi, Masahiko
, p. 13820 - 13823 (2020)
RhCl3 catalyzed the exchange reaction of disulfides and hypodiphosphoric acid tetraalkyl esters in water under homogeneous conditions, which indicated the hypodiphosphoric acid tetraalkyl esters to be novel and efficient phosphorylation reagent
Ionization of the PH Bond in Diethyl Phosphonate
Lewis, Edward S.,Spears, L. Gene
, p. 3918 - 3921 (1985)
Diethyl phosphonate is oxidized by halogens in a reaction subject to general base catalysis when the halogen concentration is sufficiently high.Under these conditions the reaction is zero order in iodine or bromine and the Broensted exponent, β, is, contrary to earlier reports, about 0.7.When the halogen concentration is quite low, but still within the range of the spectrophotometric analysis used, a third-order rate law is obeyed and the product of the ionization constant of the phosphonate and the rate constant for the reaction of the anion with halogen (which is probably diffusion controlled) can be derived.This gives an acid dissociation constant of 2.5*10-15.When the diethyl phosphonate is exchanged with D2O, a substantial kinetic isotope effect is observed for the oxidation, again contrary to expectation from previous reports on a similar reaction.This reaction is thus closely analogous to the ionization of hydrogen α to a carbonyl group or a nitro group in all of which the proton transfer is slower than the diffusion-controlled rate in both directions.
Diethyl Isopropyl and Isopropenyl Phosphate via Differently Generated Ketyl Radicals of Acetone Reacting with Diethyl Phosphoric Acid
Schole, Juergen,Schole, Christine,Eikemeyer, Juergen,Krebs, Hans Christoph
, p. 1125 - 1128 (1994)
Photochemically excited acetone reacts in 1,2-dimethoxy ethane with diethyl phosphoric acid to diethyl isopropyl phosphate.The same product is formed by reduction of acetone with magnesium amalgam in benzene in the presence of the same phosphoric acid derivative.Thermal decomposition of tetramethyldioxetane in benzene in the presence of diethyl phosphoric acid appears to yield primarily diethyl isopropenyl phosphate.
Synthesis and structure of complexes of phosphorus pentachloride with 4-dimethylaminopyridine and n-methylimidazole
Pipko, Sergey E.,Bezgubenko, Ludmila V.,Sinitsa, Anatoliy D.,Rusanov, Eduard B.,Kapustin, Evgeniy G.,Povolotskii, Mark I.,Shvadchak, Volodymyr V.
, p. 171 - 177 (2008)
Complexes of phosphorus pentachloride with 4-dimethylaminopyridine and N-methylimidazole were synthesized. The molecular structure of the phosphorus pentachloride complex with N-methylimidazole was determined by single-crystal X-ray diffraction. In the cationic part of the complex, the phosphorus atom possesses four P - Cl bonds within the range 2.109-2.148 A and two cis-P-N bonds (1.811 and 1.832 A) with N-methylimidazole and exhibits slightly distorted octahedral coordination with angles at phosphorus atom in the range 87.57°-91.50°. The relative stability of the cis and trans conformations of the complex was studied by DFT calculations. The chemical properties and reactivity of the compounds obtained are determined; their utility as condensing agents in the synthesis of amides from acids and amines was shown.
Wireless Hazard Badges to Detect Nerve-Agent Simulants
Zhu, Rong,Azzarelli, Joseph M.,Swager, Timothy M.
, p. 9662 - 9666 (2016)
Human exposure to hazardous chemicals can have adverse short- and long-term health effects. In this Communication, we have developed a single-use wearable hazard badge that dosimetrically detects diethylchlorophosphate (DCP), a model organophosphorous cholinesterase inhibitor simulant. Improved chemically actuated resonant devices (CARDs) are fabricated in a single step and unambiguously relate changes in chemiresistance to a wireless readout. To provide selective and readily manufacturable sensor elements for this platform, we developed an ionic-liquid-mediated single walled carbon nanotube based chemidosimetric scheme with DCP limits of detection of 28 ppb. As a practical demonstration, an 8 h workday time weighted average equivalent exposure of 10 ppb DCP effects an irreversible change in smartphone readout.
Broad-Spectrum Liquid- and Gas-Phase Decontamination of Chemical Warfare Agents by One-Dimensional Heteropolyniobates
Guo, Weiwei,Lv, Hongjin,Sullivan, Kevin P.,Gordon, Wesley O.,Balboa, Alex,Wagner, George W.,Musaev, Djamaladdin G.,Bacsa, John,Hill, Craig L.
, p. 7403 - 7407 (2016)
A wide range of chemical warfare agents and their simulants are catalytically decontaminated by a new one-dimensional polymeric polyniobate (P-PONb), K12[Ti2O2][GeNb12O40]?19 H2O (KGeNb) under mild conditions and in the dark. Uniquely, KGeNb facilitates hydrolysis of nerve agents Sarin (GB) and Soman (GD) (and their less reactive simulants, dimethyl methylphosphonate (DMMP)) as well as mustard (HD) in both liquid and gas phases at ambient temperature and in the absence of neutralizing bases or illumination. Three lines of evidence establish that KGeNb removes DMMP, and thus likely GB/GD, by general base catalysis: a) the k(H2O)/k(D2O) solvent isotope effect is 1.4; b) the rate law (hydrolysis at the same pH depends on the amount of P-PONb present); and c) hydroxide is far less active against the above simulants at the same pH than the P-PONbs themselves, a critical control experiment.
Prodrugs of butyric acid. Novel derivatives possessing increased aqueous solubility and potential for treating cancer and blood diseases
Nudelman, Abraham,Gnizi, Elisheva,Katz, Yifat,Azulai, Revital,Cohen-Ohana, Mirit,Zhuk, Regina,Sampson, Sanford R,Langzam, Leah,Fibach, Eitan,Prus, Eugenia,Pugach, Victoria,Rephaeli, Ada
, p. 63 - 74 (2001)
The synthesis and biological activities of acidic, basic and neutral types of butyric acid (BA) prodrugs possessing increased aqueous solubility are described. The compounds are butyroyloxyalkyl derivatives of carboxylic acids, which possess functionalities suitable for aqueous solubilization. The anticancer activity of the prodrugs in vitro was evaluated by examining their effect on the growth of human colon, breast and pancreatic carcinoma cell lines, and their solubility in aqueous media was determined. The most promising compounds, with respect to activity and solubility, were found to be the butyroyloxymethyl esters of glutaric 2a and nicotinic acids 4a and phosphoric acid as its diethyl ester 10a, which displayed IC50 values of 100 μM or lower. These prodrugs are expected to release formaldehyde upon metabolic hydrolysis. The corresponding butyroyloxyethyl esters (2b, 4b and 10b) that release acetaldehyde upon metabolism were significantly less potent. A similar correlation was observed for growth inhibition of the human prostate carcinoma cell lines PC-3 and LnCap and for induction of differentiation and apoptosis in the human myeloid leukemia cell line HL-60. The higher biological activity of the formaldehyde-releasing prodrugs 2a and 10a was further confirmed when induction of hemoglobin (Hb) synthesis in the human erythroleukemic cell line K562 was measured. Moreover, a therapeutic index (IC50/ED50) of ca. 5 was observed. The acute i.p. toxicity LD50 in mice for 2a, 2b, 10a and 10b was similar and in the range of 400-600 mg kg-1. The results obtained support the potential use of the butyric acid prodrugs for the treatment of neoplastic diseases and β-globin disorders.
Does phosphoryl protonation occurs in aqueous phosphoesters solutions
Azema,Ladame,Lapeyre,Zwick,Lakhdar-Ghazal
, p. 287 - 292 (2005)
Ionisation of trimethylphosphate (TMP), dimethylphosphate (DMP) and diethylphosphate (DEP) is investigated by acidic titration in water by Raman (R), Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopies. The vibrational frequencies of the PO2- ionic form and the neutral form were found in accord with the literature. While increasing further H+ concentration, the PO band disappears in the benefit of new ones. These results, together with deuteration experiments indicate the presence of a new ionic form positively charged with general formula R1R2R3P(OH)+ or R 1R2P(OH)+2. The pK of this phosphonium entities is lying in the range -2, -4. These results were confirmed by 31P NMR titration. The occurrence of such a phosphonium ion in aqueous solutions might be of crucial importance for biochemical reactions and interactions, owing to the large spread of phosphoryl group in biomolecules and keeping in mind that intracellular compartments are more likely concentrated media with little free water than real aqueous solutions. Furthermore, pK's can be shifted by physical-chemical parameters like dielectric constant and electric field. This may involve at least fractional positive charge apparition that might be important in biochemical regulation by charge-charge and charge-dipole interactions. This finding will gain to be further explored on more complex molecules like phospholipids, nucleic acids and proteins.
Effect of the molecular size of analytes on polydicetylene chromism
Seo, Donghwan,Kim, Jinsang
, p. 1397 - 1403 (2010)
The pH chromism of polydiacetylenes (PDAs) is examined with respect to the molecular size and acidity of acid analytes, along with the alkyl spacer length of primary-amine-functionalized diacetylene (DA) lipids. pH turns out to be an important parameter to charge amine headgroups of PDA but a change in pH does not necessarily result in a PDA color change. The molecular size of acid analytes is identified as another factor that can produce a configurational change in PDA amine headgroups, followed by perturbation of the ene-yne conjurgated backbone.In addtion. the length of a alkyl spacer between the amine headgroup and the amide group of the diacetylene lipids is found to strongly affect thedegree of PDA chromatic transition. The longer alkyl spacer shows a smaller chromatic transition from blue to red phase. The alkyl spacer seems to provide a certain degree of freedom to the amine headgroup, thus decreasing the transfer of headgroup steric effects to the PDA backbone. These correlations found for PDA; chromism are applied, to, he development of a system that colori metrically detects diethyl phosphate (DEP), a degraded nerve agent simulant. PDA liposomes show a selective chromatic transition upon binding with DEP compared to other acid analytes.
Kinetic and isotope effect studies on the intermediacy of ethyl metathiophosphate in ethanolysis of O-ethyl N-1-adamantyl phosphoramidothioate
Jankowski, Stefan,Quin, Louis D.,Paneth, Piotr,O'Leary, Marion H.
, p. 23 - 27 (1997)
The fragmentation of O-ethyl N-l-adamantylphosphoramidothioate (1a) and its oxygen counterpart 1b was examined in ethanol at 65-100°C. The solvent hydrogen effect kEtOH/kEtOD and kinetic nitrogen effect k14/k15 were determined at 80°C. The rates and parameters of activation of ethanolysis of 1a and 1b are slightly different. The solvent effect kEtOH/kEtOD was found to be equal to 0.84 ± 0.05 for 1a and 0.83 ± 0.04 for 1b. The nitrogen effect k14/k15 was found to be sensitive to replacement of sulfur by oxygen, and equal to 1.0083 ± 0.0004 for 1a and 1.0065 ± 0.0006 for 1b. The data indicate that proton transfer from the OH group to the amine moiety precedes the P-N bond breakage. The kinetic nitrogen isotope effect for the amine elimination recalculated for the pre-equilibrium step is equal to 1.0232 for 1a and 1.0215 for 1b. These results are consistent with the intermediacy of ethyl metathiophosphate in the solvolysis of 1a.
