It is shown by proton NMR and quantum chemical PCILO calculations that monothio-β-ketones in solution exist as different isomers depending on substituents, solvent and temperature. In solvents with low dielectric constants the hydrogen-bridged cis enol form predominates, and is in fast equilibrium (in the NMR scale) with nonchelated trans enol forms down to ?100°C at least. Transition enthalpies are of the order of 7–15 kJ mol?1. In compounds with R2 = Me the rotation of the Me -CS group around the neighbouring C-C- bond can be detected and the thermodynamic and kinetic parameters estimated. The reason for the slowing down of this rotation, inferred from the line broadening in NMR, is probably the stabilization of a trans isomer by interaction between the protons of the methyl group and the lone pairs of the oxygen atom. There are no indications for the presence of chelated and non-chelated enethiol isomers from the PMR studies and quantum chemical calculations performed. 相似文献
We used a combination of theoretical and experimental methods to derive the spectroscopic properties of imidazolium-based ionic liquids. Vibrational frequencies, NMR chemical shifts, and quadrupole coupling constants react in comparable manner to changes in the chemical environment. This suggests that both the IR and the NMR spectroscopic properties reflect a similar type of electronic perturbation caused by hydrogen bonding. These relationships of the spectroscopic properties provide detailed information about structural complexes and may thus serve as good indicators of ion-pair formation. They also help to decide which spectroscopic tool is the most sensitive for investigating molecular interactions. The measurement of only one spectroscopic property allows the prediction of other properties that cannot be so easily measured. In some cases, this is the only way to obtain reliable coupling constants for deriving molecular correlation times from macroscopic NMR relaxation times, thus opening a new path for studying structure-dynamics relations in ionic liquids. 相似文献
Further examples of the α-aminoalkylation of white phosphorus and of a biphosphine are reported. The reaction is described using C-methyl piperidines, methylamine, ethylamine or propylamine as the amine component, and formaldehyde or benzaldehyde as the carbonyl component. The reaction mechanism has been clarified. Furthermore the direct synthesis of the diethylamine salt of phosphorous acid is reported. In addition, some physical and chemical properties of tris (dialkylamino-methyl)-phosphine oxides are given and their coordination compounds with nickel halides are described. 相似文献
2-Vinylindole ( 1a ) and its donor- and acceptor-substituted (E)-derivatives 1b – e react highly locoselectively with dimethyl 1,2,4,5-tetrazine-3,6-dicarboxylate ( 3 ) to form the novel (indol-2-yl)-1,4-dihydropyridazines 4a and 7 as well as the heterocyclic annellated pyridazines 4b , 5 , and 6 . The reactions of the structurally related 3-vinylindoles 2a – e with 3 also gave rise to new indol-3-ylpyridazines 8 , 9 , and 10 . The locoselectivities of these Diels-Alder reactions were controlled mainly by steric effects. 相似文献
Determination of traces of iridium with thiodibenzoylmethane by substoichiometric isotope dilution analysisIridium(III or IV) reacts with thiodibenzoylmethane on heating at pH 6 to form a 1:3 complex, which can be concentrated by extraction into chloroform. Based on this reaction, a reproducible, selective determination of iridium is achieved by means of substoichiometric isotope dilution analysis, based on 192Ir. The linear range is 1–11 nmol of iridium. 相似文献
Harary [8] calls a finite, simple graphG asum graph if one can assign to eachviV(G) a labelxi so that{vi,vj}E(G) iffxi+xj=xk for somek. We generalize this notion by replacing xi+xj with an arbitrary symmetric polynomialf(xi,xj). We show that for eachf, not all graphs are f-graphs. Furthermore, we prove that for everyf and every graphG we can transformG into anf-graph via the addition of |E(G)| isolated vertices. This result is nearly best possible in the sense that for allf and for
, there is a graphG withn vertices andm edges which, even after the addition ofm-O(n logn) isolated vetices, is not andf-graph.Research supported in part by a U.S.A.-Israel Binational Science Foundation and by a Bergmann Memorial Grant.Research supported in part by the Office of Naval Research contract number N00014-85-K0622. 相似文献
Aryl 2-[(2-imidazolyl)ethyl or 3-(2-imidazolyl)propyl]ketones were ketalized by glycerol or 3-mercapto-1,2-propanediol in boiling benzene in the presence of 4-toluenesulfonic acid to provide the title compounds. The aryl substituents are 4-chloro-, 4-bromo-, 4-fluoro-, or 2,4-dichlorophenyl. While aryl (2-imidazolyl)methyl ketones condensed with glycerol to form cis- and trans-{2-aryl-2-[(2-imidazolyl)methyl]-4-(hydroxymethyl)}-1,3-dioxolanes, related condensations with 3-mercapto-1,2-propanediol, under similar, or even more stringent reaction conditions, produced no 1,3-oxathiolane analogs, with the starting ketones being recovered. Separation and structure determination of these racemic cis and trans isomeric products are described. The structure of these stereoisomers was established by means of 1H and 13C nmr correlation and nOe experiments. Selective methylation of the N-unsubstituted 2-imidazolyl alcohols with one equivalent sodium hydride and methyl iodide provided the corresponding N-methyl alcohols in excellent yields. With excess benzoyl chloride, N-unsubstituted 2-imidazolyl alcohols were initially converted to O, N-dibenzoates from which the N-benzoyl group was easily cleaved by ammonium hydroxide in ethanol to provide benzoate esters. 相似文献
The wood-degrading fungus Trametes multicolor secretes several laccase isoforms when grown on a simple medium containing copper in the millimolar range for stimulating
laccase synthesis. The main isoenzyme laccase II was purified to apparent homogeneity from the culture supernatant by using
anion-exchange chromatography and gel filtration. Laccase II is a monomeric glycoprotein with a molecular mass of 63 kDa as
determined by sodium dodecylsulfate polyacrylamide gel electrophoresis, contains 18% glycosylation, and has a pI of 3.0. It oxidizes a variety of phenolic substrates as well as ferrocyanide and iodide. The pH optimum depends on the substrate
employed and shows a bell-shaped pH activity profile with an optimum of 4.0 to 5.0 for the phenolic substrates, while the
nonphenolic substrates ferrocyanide and 2,2′-azino-bis(3-ethylbenzthiazoline-6-sulfonate) show a monotonic pH profile with
a rate decreasing with increasing pH. 相似文献