New sources of “active” halogen bis(dialkylamide)hydrogen dibromobromates, efficient reagents for destruction of ecotoxicants

Bis(dialkylamide)hydrogen dibromobromates were synthesized and their reactivity was investigated in decomposition of diethylphosphonic, diethylphosphoric, and 4-toluenesulfonic acids 4-nitrophenyl esters. The nucleophilic reactivity of a typical α-nucleophile, hypobromite ion, is independent of the source of the active bromine. The cetyltrimethylammonium dibromobromate is a unique reagent for destruction of ecotoxicants. In weakly alkaline media the half-life of 4-nitrophenyl diethylphosphonate did not exceed 6 s at [BrO^?] 0.02 mol l^?1, and the apparent reaction rate compared to water increased ～40-fold. The main factor governing the micellar effects of surfactants is concentrating the substrate in the micellar pseudophase.     

Micellar effects of surfactants in cleavage of 4-nitro-phenyl diethyl phosphonate by hydroperoxide anion

We have studied the nucleophilicity of the hydroperoxide anion relative to 4-nitrophenyl diethyl phosphonate (NPDEPS) in the presence of cetyltrimethylammonium bromide (water, 25 °C) while varying the acidity of the medium and the hydroperoxide anion concentration over a broad range. The increase in the reaction rate when the reaction is transferred to a micellar pseudophase is as high as ∼10-fold, which is explained by concentration effects. In CTAB micelles, as in water, the hydroperoxide ion is one of the most effective α-nucleophiles, and the size of the α-effect, characterized by the ratio of the second-order rate constants for reactions of HOO⁻ and OH⁻ anions with NPDEPS, remains practically constant and reaches a value of ∼50-fold. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 6, pp. 357–363, November–December, 2006.     

Nonlinear Brönsted relationships and the α-effect of oximate ions in acyl* transfer reactions

A detailed extrathermodynamic analysis of the behavior of oximate ions (pK_a≈7–13) in reactions with various types of substrate was undertaken. For oximate ions with pK_a≥9.0, irrespective of the nature of the acyl group, the reactivity of the oximes tends toward that of the alcoholate ions, and their α-effect disappears. The reason for this is the unfavorable solvation effects of the solvent. Institute of Physical Organic Chemistry and Coal Chemistry, National Academy of Sciences of Ukraine, 70 R. Lyuksemburg ul., Donetsk 340114, Ukraine. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 34, No. 2, pp. 86–90, March–April, 1998.     

Micelle Effects of Functionalized Surfactants, 1-Cetyl-3-(2-hydroxyiminopropyl)imidazolium Halides,in Reactions with p-Nitrophenyl p-Toluenesulfonate,Diethyl p-Nitrophenyl Phosphate,and Ethyl p-Nitrophenyl Ethylphosphonate

1-Cetyl-3-(2-hydroxyiminopropyl)imidazolium chloride and bromide were synthesized for the first time. These compounds are functionalized zwitterionic surfactants which give rise to micelle formation in aqueous solution. Kinetic and thermodynamic analysis of nucleophilic cleavage of p-nitrophenyl p-toluenesulfonate, diethyl p-nitrophenyl phosphate, and ethyl p-nitrophenyl ethylphosphonate in the presence of 1-cetyl-3-(2-hydroxyiminopropyl)imidazolium halide micelles showed that the latter are powerful nucleophilic reagents whose kinetic behavior can be described in terms of a simple pseudophase distribution model. The efficiency of substrate solubilization with zwitterionic surfactant micelles and the reactivity of the oximate fragment in the micelle phase were estimated on a quantitative level. The observed acceleration of S_N2 reactions with the examined p-nitrophenyl esters relative to analogous reactions of zwitterionic 1-methyl-3-(2-hydroxyiminopropyl)imidazolium halides is, respectively, 12800, 550, and 900 times; it is explained mainly by increased concentration of the reactants in micelles.     

Doppler three-level (V-scheme) laser without population inversion

The theory of amplification and lasing without population inversion in a three-level medium with inhomogeneous broadening via the formation of an open V configuration is elaborated. The conditions for energy transfer from the infrared into the visible spectral range, i.e., the conditions of up-conversion n _b >n _c >n _a , and the external field required for saturation of the b?a transition are established. Two-photon resonant Raman transitions in ensemble of mobile atoms of a gas-discharge plasma are analyzed. The frequency shift of the probe field spectrum as a whole is shown to be governed by the frequency shift of the pump field multiplied by the ratio of the wave numbers of the probe amplification field and the pump field. The interaction of atoms through Ne transitions with the pump field (λ=1.15 εm, 2p ₄-2s ₂ transition) and the lasing field (λ=0.6328 εm, 3s ₂-2p ₂ transition) with an increase in the lasing frequency by a factor of 1.82 with respect to the absorbed radiation is calculated.     

Micellar Effects of Functional Detergents – 1-Cetyl-3-(2-hydroxyiminopropyl)imidazolium Halides – in Reactions with 4-Nitrophenyl Toluenesulfonate and 4-Nitrophenyl Diethyl Phosphate

An anomalously large increase was found in the rate of cleavage of 4-nitrophenyl 4-toluenesulfonate (13000 times) and diethylphosphate (550 times) by the zwitterionic micelles of 1-cetyl-3-(2-hydroxyiminopropyl)imidazolium chloride and bromide. Detailed kinetic and thermodynamic analysis of these processes made it possible to establish that the main factor responsible for the high rates of reaction in the micellar phase is the concentration of the reagents.