Kinetics of the cycloaddition of maleic anhydride to arylaminomethylene derivatives of 3-methyl-1-phenylpyrazole-5-thione

1986 ◽  
Vol 22 (5) ◽  
pp. 503-507 ◽  
Author(s):  
I. Ya. Kvitko ◽  
I. I. Potanochkina ◽  
L. A. Brindza
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.


Studies of the catalytic oxidation of benzene to maleic anhydride and carbon dioxide over vanadia/molybdena catalysts show that the major part of the reaction involves interacting gas and gas-solid processes. The results are consistent with a mechanism in which a benzeneoxygen adduct is formed catalytically, desorbs and then reacts to give maleic anhydride entirely in the gas phase. On the basis of this proposed mechanism, the kinetics of individual reactions have been investigated in some depth. The over-oxidation of maleic anhydride has been found to be not significant under the conditions of reaction. The kinetic relationships governing the homogeneous decomposition of the adduct and the oxidation of the adduct to maleic anhydride and to carbon dioxide have been established. The results show that essentially all of the anhydride originates from mixed gas-solid/gas reaction while substantial amounts of carbon dioxide are produced entirely catalytically.


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.


2003 ◽  
Vol 107 (43) ◽  
pp. 9249-9249 ◽  
Author(s):  
Evgeni M. Glebov ◽  
Larisa G. Krishtopa ◽  
Victor Stepanov ◽  
Lev N. Krasnoperov

Catalysts ◽  
2021 ◽  
Vol 11 (9) ◽  
pp. 1102
Author(s):  
Wojciech Baran ◽  
Ewa Masternak ◽  
Dominika Sapińska ◽  
Andrzej Sobczak ◽  
Ewa Adamek

The aim of our study was to assess the possibility of using the photocatalytic process conducted in the presence of TiO2 to obtain new stable derivatives of antibacterial drugs. The possibility of introducing hydroxyl, chlorine, or bromide groups into antibiotics molecules was investigated. The experiments were conducted in aqueous solutions in the presence of TiO2-P25 as a photocatalyst, Cl− and Br- ions, and antibiotics belonging to eight different chemical classes. All experiments were initiated by UVa radiation. The kinetics of photocatalytic reactions and their quantum yield were determined, and the stable products were identified. All of the antibiotics used in the experiments underwent a photocatalytic transformation, and the quantum yields were in the range from 0.63 to 22.3%. The presence of Br- or FeCl3 significantly increased the efficiency of the photocatalytic process performed in the presence of TiO2, although Br- ion also acted as an inhibitor. Potentially biologically active chlorine derivatives from Trimethoprim, Metronidazole, Chloramphenicol, and bromine derivatives from Trimethoprim, Amoxicillin were obtained under experimental conditions. The potentially inactive halogen derivatives of Sulfamethoxazole and hydroxyl derivatives described in the literature were also identified.


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