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71.
Lakshminarasimhan Damodharan 《Tetrahedron letters》2004,45(51):9427-9429
Database analysis on H ? H interactions of the type CH2 ? H2C and N-H ? H-N in organic crystals substantiate the occurrence of dihydrogen bonds in the absence of metal atoms. 相似文献
72.
The semi-empirical quantum chemical MNDO-PM3 calculations of the enthalpies of formation of Meisenheimerortho- andipso--complexes of 1,3,5-trinitrobenzene (TNB) and 2,4,6-trinitrotoluene (TNT) with the phenoxide anion in the gas phase and in water are performed within the framework of the point dipole model. Based on the calculated heats and activation barriers to substitution of the nitro group by the phenoxyl group in TNB and TNT, the possibility of the reactions of TNB and TNT with the phenoxide anion in water is shown. These reactions in water occurvia the SNAr mechanism involving the correspondingipso--complex as an intermediate. In the gas phase, the SNAr mechanism is impossible, because the reaction is strongly endothermic. In the case of TNT, the exothermic reaction of elimination of a proton from the methyl group by the phenoxide anion competes with nucleophilic substitution in a polar solvent. The activation energy calculated for this exothermic reaction is 8 kcal mol–1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 624–628, April, 1995. 相似文献
73.
A new organic photochromic compound containing pyrazolone-ring photochromic functional unit: 1-phenyl-3-methyl-4-benzyl-5-one pyrazole S-methyl thiosemicarbazone (PMBP-smtsc) was synthesized. The photochromic properties and photochemical kinetics of PMBP-smtsc have been studied by UV reflectance spectra under irradiation of 365 nm light. The crystal structure analyses of photocolored product show the photochromism is due to the photoisomerization from enol form to keto form through an intermolecular proton transfer. 相似文献
74.
In this paper, 2-(2′-hydroxy-phenyl)-4(3H)-quinazolinone (HPQ), a typical compound that exhibits excited state intramolecular proton transfer (ESIPT) reaction and possesses good photophysical properties, is synthesized and used as fluoroionophore for Fe3+ sensitive optochemical sensor. The decrease of fluorescence intensity of HPQ membrane upon the addition of Fe3+ was attributed to the blocking of ESIPT reactions of HPQ and quenching its fluorescence. The effect of the composition of the sensing membrane was studied, and experimental conditions were optimized. The sensor shows a linear response toward Fe3+ in the concentration range of 7.1 × 10−7 M to 1.4 × 10−4 M with a limit of detection of 8.0 × 10−8 M, and a working pH range from 2.5 to 4.5. It shows excellent selectivity for Fe3+ over a large number of cations such as alkali, alkaline earth and transitional metal ions. The proposed sensor is applied to the determination of the content of iron ions in pharmaceutical preparations samples with satisfactory results. 相似文献
75.
76.
Proton NMR was used to study the complexation reaction between silver ion and hexathia-18-crown-6 in a number of binary mixed solvents of dimethyl sulfoxide with acetonitrile and methanol. Formation constants for the resulting 1:1 complexes in different solvent mixtures were determined by computer fitting of the chemical shift-mole ratio data. The influence of solvent composition on the stability of the resulting complex is discussed. The exchange kinetics of Ag+-hexathia-18-crown-6 in 70-30 wt.% dimethyl sulfoxide-acetonitrile and 75-25 wt.% dimethyl sulfoxide-methanol were studied by proton NMR line-shape analysis. In both solvent mixtures, the exchange of thiacrown ether between the free and complexed sites was found to proceed via a dissociative pathway. The exchange rates and the activation parameters E
a, H
, S, and G for the ligand exchange were determined and the influence of solvent properties on these parameters discussed. 相似文献
77.
A new mechanism and formalism for proton transfer in donor-acceptor complexes with long hydrogen bonds introduced recently [1], is applied to a proton transfer in liquid water. Structural diffusion of hydroxonium ions is regarded as totally adiabatic process, with synchronous hindered translation of two closest water molecules to and from the reaction complex as crucial steps. The water molecules induce a gated shift of the proton from the donor to the acceptor in the double-well potential with simultaneous breaking/formation of hydrogen bonds between these molecules and the proton donor and acceptor. The short-range and long-range proton transfer as structural diffusion of Zundel complexes is also considered. The theoretical formalism is illustrated with the use of Morse, exponential, and harmonic molecular potentials. This approach is extended to proton transfer in strongly hydrogen-bonded donor-acceptor complexes. In contrast to the above model [1], the short hydrogen bond between the donor and acceptor moieties, however, completely erodes the barrier along the proton transfer mode. This introduces some physical pattern differences from proton transfer reactions in truly double-well potentials with a finite proton transfer barrier at the transition configuration with respect to the environmental nuclear coordinates. The differences apply particularly to the origin of the kinetic isotope effect. We discuss explicitly details of the excess proton conductivity in aqueous solution, but the concepts and formalism apply broadly to acid-base reactions, proton conduction channels, and other strongly hydrogen-bonded O- and N-proton donor-acceptor systems. 相似文献
78.
Alkylation of 8-dimethylamino-1-methylamino-4-nitronaphthalene in the CD3I/KOH/DMSO system afforded a 4-nitro derivative containing the N(CD3)Me group in position 1. Direct proof of the structure of the intramolecular hydrogen bond in solutions of monoprotonated
4-R-1,8-bis(dimethylamino)naphthalenes was obtained for the first time. 1H NMR study revealed that the chelated NH proton is shifted to the N(8) atom for R = NO2 and NH3
+ and to the N(1) atom for R = NH2.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 159–162, January, 2006. 相似文献
79.
Isolated polyfluorobenzene (PFB) molecules and their protonated forms are investigated by the AM1 method with full geometry optimization. The proton affinities of PFB are estimated for different protonated positions. The proton affinity of PFB averaged over all isomers is shown to decrease monotonically as the number of fluorine atoms in the molecule increases. The relative populations of different isomers of arenonium ions (AI) formed by PFB protonation are determined. From the calculated data, the value of + for the F atom in theipso-position is estimated as 1.00. The activation energies of the 1,2-hydrogen shifts in AI are calculated. The dependences of the proton affinity and the activation energies of 1,2-hydrogen shifts on the number of halogen atoms are found to have distinct characters for PFB and polychlorobenzenes. The physical reasons for these difference are discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1878–1882, November, 1993. 相似文献
80.
Hiromi Matsushita Ritsuko Nagao Masayuki Nogami Toshihiro Kasuga Tomokatsu Hayakawa 《Journal of Sol-Gel Science and Technology》2000,19(1-3):559-562
High proton-conducting P2O5-SiO2 glass was applied to the electrolyte of the hydrogen concentration cell for hydrogen gas sensing. 5P2O5·95SiO2 glass was prepared using the sol-gel method and its electrical conductivity and electromotive force were measured at 50°C as a function of both the ambient humidity and hydrogen gas concentration. The electrical conductivities increased with increasing humidity and reached 10–2 S/cm at 90% relative humidity. The electromotive force of the hydrogen concentration cell, where the glass was used as a membrane, showed good Nernstian response to hydrogen pressure in the high relative humidity region. 相似文献