Chiral methylbenzylammonium salts of aryldithiophosphonic acids containing glucofuranose,allofuranose, and galactopyranose diacetonide scaffolds

Abstract

New chiral methylbenzylammonium salts of aryldithiophosphonic acids containing glucofuranose, allofuranose, and galactopyranose diacetonide substituents were obtained using (S)-(–)-α-methylbenzylamine, (R)-(+)-α-methylbenzylamine, and (R,S)-(±)-α-methylbenzylamine. Salts obtained possess antimicrobial activity.     

Electrochemical Oxidation of Disulfides Derived from Isocyanuric Acid

Anodic oxidation of linear and bicyclic disulfides derived from isocyanuric acid was studied by cyclic voltammetry and numerical simulation. The PM3 molecular modeling revealed three types of the highest occupied molecular orbitals determining the electrochemical reactivity of these compounds: n electrons of the sulfur atoms of the disulfide bridge in linear and N-Me- and N-Ph-substituted bicyclic disulfides, π electrons of the aromatic fragment in the disulfide with the N-2-(2-methoxyphenoxy)ethyl isocyanurate substituent, and n electrons of the sulfide sulfur atoms in the compound with the -SS- and -S- fragments in the aliphatic chain. Oxidation of the disulfides with the SS-localized highest occupied molecular orbital follows the scheme with reversible electron transfer, followed by a fast potential-determining second-order reaction and a slow current-determining first-order reaction (ECC mechanism). The isocyanurate heterocycle does not participate directly in redox transformations but stabilizes the electrochemically generated radical cations by the mechanism of transannular interaction.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 3, 2005, pp. 422–429.Original Russian Text Copyright © 2005 by Grogger, Fattakhov, Jouikov, Shulaeva, Reznik.     

One-Pot Synthesis of Quaternary Phosphonium Salts Based on Tertiary Phosphines and (R)-(+)-Pulegone

Russian Journal of General Chemistry - As a result of reactions of nucleophilic addition of tertiary phosphines to pulegone in the presence of hydrochloric acid, quaternary phosphonium salts were...     

2,4-diamino-6-(acetohydrazidomethylsulfinylmethyl)-1,3,5-triazine. State in solution, acid-base and complexing properties

Solutions of a new drug, 2,4-diamino-6-(acetylhydrazidomethylsulfonylmethyl)-1,3,5-triazine, exhibiting tuberculocidal activity were studied using the methods of pH-metry, spectrophotometry, mathematical simulation of equilibria (CPESSP software), and molecular mechanics. Protolytic properties of the compound in the medium of aqueous dimethylsulfoxide (40 vol % of DMSO) were characterized. The composition of the copper(II) complex of this compound was determined and its stability constants were calculated. Based on the absorption spectra in the UV and visible regions the complexing ability of 2,4-diamino-6-(acetylhydrazidomethylsulfonylmethyl)-1,3,5-triazine toward nickel(II) and cobalt(II) were characterized in comparison with copper(II) under the same conditions.     

Synthesis of 1-Alkyl 3,5-Bis(ω-mercaptoacetoalkyl) Isocyanurates and Macrocyclic Disulfides Derived Thereof

1-Alkyl 3,5-bis(-hydroxyalkyl) isocyanurates were reacted with mercaptoacetic acid to obtain 3,5-bis(-mercaptoacetoxyalkyl) isocyanurates whose oxidation gives rise to macrocyclic disulfides.     

Solution state and complexing ability of 1,4-bis(amidomethylsulfinyl)butane toward iron(III), copper(II), cobalt(II), nickel(II), and manganese(II)

The solution state and thermodynamic stability of complexes of the new antituberculosis agent 1,4-bis(amidomethylsulfinyl)butane (L) with iron(III), copper(II), cobalt(II), nickel(II), and manganese(II) in an aqueous solution in the presence and in the absence of the nonionic surfactant Brij 35 were studied by spectrophotometry, pH potentiometry, NMR relaxation technique (T = 25 °C; variable ionic strength), and mathematical simulation. The geometry optimization of all structures was carried out by the molecular mechanics method MM2 in order to obtain data on coordination modes. In addition, the structure of 1,4-bis(amidomethylsulfinyl)butane was refined by the DFT/B3LYP/6-311++G(d,p) quantum chemical method using the IEFPCM model to take into account solvent effects. In an aqueous solution (in the concentration range of 1.3?10^–5—1?10^–3 mol L–1) and in the presence of Brij 35, 1,4-bis(amidomethylsulfinyl)butane exists as a neutral monomer. The Beer—Lambert—Bouguer law is obeyed in a wide concentration range for compound L in an aqueous solution, as well as in the presence of the surfactant, which can be used for the quantification of compound L. Iron(III), cobalt(II), and nickel(II) were shown to form 1: 1 mononuclear complexes with L; and copper(II) forms, 1: 1 and 2: 2 complexes. The presence of Brij 35 in the Cu²⁺—L system at a micellar concentration promotes the formation of a dinuclear complex.     

1,6-Bis(hydrazidomethylsulfinyl)hexane: the solution state and complexation with copper(II)

Russian Chemical Bulletin - The solution state of a new antituberculosis drug 1,6-bis(hydrazidomethylsulflnyl)hexane (L) and its complexation with copper(II) were investigated by spectrophotometry,...     

Chiral S‐stannyl dithiophosphates and dithiophosphonates on the basis of monoterpenols

Chiral S‐tributylstannyl dithiophosphates and dithiophosphonates were obtained by the reactions of optically active dithiophosphoric and dithiophosphonic acids containing (S)‐(–)‐menthyl and (R)‐(+)‐menthyl substituents with gaseous ammonia and tributyl chlorostannane. The reactions of chiral ammonium dithiophosphate containing (1R)‐endo‐(+)‐fenchyl substituent with tributyl chlorostannane or tetrachlorostannane result in corresponding S‐tributylstannyl dithiophosphate or tetrakis(dithiophosphato)stannane. Molecular structure of ammonium O,O‐di‐(–)‐menthyldithiophosphate was studied by X‐ray single crystal diffraction. Bactericidal activity of S‐tributylstannyl dithiophosphates was tested.     

New biologically active phosphonium salts based on 3-(diphenylphosphino)propionic acid and unsaturated amides

Russian Chemical Bulletin - New carboxylate phosphabetaines were synthesized from 3-(diphenylphosphino)propionic acid and unsaturated amides. Alkylation of the synthesized carboxylate...     

Synthesis and oxidation of sulfides containing an isocyanurate fragment

The reaction of 1-(ω-haloalkyl)-3,5-dimethylisocyanurates with sodium salt of methyl thioglycolate afforded the corresponding 1-[ω-(methoxycarbonylmethylthio)alkyl]-3,5-dimethylisocyanurates, the oxidation of which with the system 34% aqueous H₂O₂-0.2 M NaHCO₃-Mn^II leads to the corresponding sulfones. The oxidation of these compounds with 34% aq. H₂O₂ in Ac₂O gives alternative products, viz., sulfones, sulfoxides, or α-acyloxy sulfides, depending on the temperature and number of methylene groups between the isocyanurate fragment and the sulfur atom.