The chemistry of some quaternary derivatives of the 10,11-dihydrodibenzo[b,f]phosphepin system. The kinetics of alkaline hydrolysis, and products of betaine collapse, and a comparison with other phosphonium salts

Author(s):  
David W. Allen ◽  
Barrie G. Hutley ◽  
A. Christopher Oades
Author(s):  
M. Stankovičová ◽  
Ž. Bezáková ◽  
J. Pavlíková ◽  
J. Mažeriková ◽  
M. Kissová ◽  
...  

1980 ◽  
Vol 45 (11) ◽  
pp. 2873-2882
Author(s):  
Vladislav Holba ◽  
Ján Benko

The kinetics of alkaline hydrolysis of succinic acid monomethyl and monopropyl esters were studied in mixed aqueous-nonaqueous media at various temperatures and ionic strengths. The results of measurements are discussed in terms of electrostatic and specific interactions between the reactants and other components of the reaction mixture. The kinetic parameters in the media under study are related to the influence of the cosolvent on the solvation sphere of the reactants.


1986 ◽  
Vol 51 (12) ◽  
pp. 2786-2797
Author(s):  
František Grambal ◽  
Jan Lasovský

Kinetics of formation of 1,2,4-oxadiazoles from 24 substitution derivatives of O-benzoylbenzamidoxime have been studied in sulphuric acid and aqueous ethanol media. It has been found that this medium requires introduction of the Hammett H0 function instead of the pH scale beginning as low as from 0.1% solutions of mineral acids. Effects of the acid concentration, ionic strength, and temperature on the reaction rate and on the kinetic isotope effect have been followed. From these dependences and from polar effects of substituents it was concluded that along with the cyclization to 1,2,4-oxadiazoles there proceeds hydrolysis to benzamidoxime and benzoic acid. The reaction is thermodynamically controlled by the acid-base equilibrium of the O-benzylated benzamidoximes.


2020 ◽  
Vol 10 (1) ◽  
Author(s):  
Jarmila Králová ◽  
Michal Jurášek ◽  
Lucie Mikšátková ◽  
Anna Marešová ◽  
Jan Fähnrich ◽  
...  

AbstractFluorescent sterol probes, comprising a fluorophore connected to a sterol backbone by means of a linker, are promising tools for enabling high-resolution imaging of intracellular cholesterol. In this study, we evaluated how the size of the linker, site of its attachment and nature of the fluorophore, affect the localization and trafficking properties of fluorescent sterol probes. Varying lengths of linker using the same fluorophore affected cell penetration and retention in specific cell compartments. A C-4 linker was confirmed as optimal. Derivatives of heterocyclic sterol precursors attached with identical C-4 linker to different fluorophores at diverse positions also showed significant differences in their binding properties to various intracellular compartments and kinetics of trafficking. Two novel red-emitting probes with good cell permeability, fast intracellular labelling and slightly different distribution displayed very promising characteristics for sterol probes. These probes also strongly labelled endo/lysosomal compartment in cells with pharmacologically disrupted cholesterol transport, or with a genetic mutation of cholesterol transporting protein NPC1, that overlapped with filipin staining of cholesterol. Overall, the present study demonstrates that the physicochemical properties of the fluorophore/linker pairing determine the kinetics of uptake and distribution and subsequently influence the applicability of final probes.


1981 ◽  
Vol 34 (2) ◽  
pp. 365 ◽  
Author(s):  
H Stunzi

The reactions of isatin-5-sulfonate anion (si-) which cause a hysteresis in pH titrations were studied by pH-metric and n.m.r, spectroscopic methods. Rapid alkalimetric titrations [I 0.15 M (KNO3),37�] gave the pKa value corresponding to the addition of OH- to si- [pKa(ring) 9.55]. The slow ring opening to the sulfonatoisatate dianion (sia2-) led to a drift of the pH values towards an equilibrium buffer region. Its pKa, value [pKa(eq) 3.44] corresponds to the reaction si-+H2O ↔ sia 2-+H+ Rapid back-titration gave the pKa value of the ring-opened species Hsia- [pKa(open) c. 1.3]. The rate law for the ring opening d[sia]/dt=k2 [siOH](OH)+k1*[si] was obtained from the rate of change of pH. N-Methylisatin-5-sulfonate behaves analogously.


Sign in / Sign up

Export Citation Format

Share Document