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81.
2-Propynamides react with aryl isocyanates in the presence of triethylamine to give 5-methylene-2,4-imidazolidinediones 5 in good yields. If the propynamide contains a terminal trimethylsilyl group, Z-trimethylsilylidenehydantoin ( 7 ) is produced. 相似文献
82.
Gary M. Coppola 《Journal of heterocyclic chemistry》1983,20(2):331-336
Reactions of 1,3-disubstituted-2,3-dihydro-1,3,2-benzodiazaphosphorin-4 (1 H)-one 2-oxides ( 1 ) with various electrophiles were investigated. The treatment of 1 with aldehydes in the absence of a basic catalyst directlyafforded alcohols 7a-h in good yield. The product from the reaction of 1 with chloral, on treatment with sodium hydride, resulted in the formation of a dichloroepoxide ( 8 ). When 1 was allowed to react with isocyanates or isothiocyanates in the presence of triethylamine, amides 10a-e and thioamide 11 were produced in good yield. Compounds 1a and 1b were readily halogenated on their phosphorus atom by treatment with either carbon tetrachloride or carbon tetrabromide and triethylamine. The P-chloro compound 12a reacted with ethanol to furnish the P-ethoxy derivative 13 and, in an attempt to react 12a with bis (2-chloroethyl) amine, anhydride 14 was formed in high yield. Spectral data for the majority of the products are also discussed. 相似文献
83.
Two points involving molecular structure have been investigated using mass spectrometry. First, mass spectra have been obtained that indicate a rapid means for differentiating bimolecular compounds from other structural isomers. Second, the mass spectrometric method has been used to evaluate bonding within bimolecular compounds. Quinone compounds have been reacted with dhydroxybenzene compounds to produce quinhydrone products, and upon mass spectrometric analysis, the quinhydrones decompose to regenerate derivatives of the starting materials. Evaluation of the decomposition products suggests that the hydroxyl hydrogens are involved in a resonance structure, and while in symmetrical quinhydrones, the hydroxyl hydrogens are probably associated equally with each reactant, unsymmetrical quinhydrones generate an unbalanced electronic distribution that eliminates the complete equivalency of the hydrogens. 相似文献
84.
Weronika Gruszka Anna Lykkeberg Gary S. Nichol Michael P. Shaver Antoine Buchard Jennifer A. Garden 《Chemical science》2020,11(43):11785
Heterometallic cooperativity is an emerging strategy to elevate polymerisation catalyst performance. Here, we report the first heterotrimetallic Na/Zn2 and K/Zn2 complexes supported by a ProPhenol ligand, which deliver “best of both” in cyclic ester ring-opening polymerisation, combining the outstanding activity (Na/K) and good control (Zn2) of homometallic analogues. Detailed NMR studies and density-functional theory calculations suggest that the Na/Zn2 and K/Zn2 complexes retain their heterometallic structures in the solution-state. To the best of our knowledge, the K/Zn2 analogue is the most active heterometallic catalyst reported for rac-lactide polymerisation (kobs = 1.7 × 10−2 s−1), giving activities five times faster than the Na/Zn2 complex. These versatile catalysts also display outstanding performance in ε-caprolatone and δ-valerolactone ring-opening polymerisation. These studies provide underpinning methodologies for future heterometallic polymerisation catalyst design, both in cyclic ester polymerisation and other ring-opening (co)polymerisation reactions.Cooperative heterotrimetallic Na/Zn2 and K/Zn2 complexes combine the excellent activities and control of the homometallic analogues, giving “best of both” in cyclic ester ring-opening polymerisation. 相似文献
85.
Analytical solutions of the lattice Boltzmann BGK model 总被引:1,自引:0,他引:1
Analytical solutions of the two-dimensional triangular and square lattice Boltzmann BGK models have been obtained for the plane Poiseuille flow and the plane Couette flow. The analytical solutions are written in terms of the characteristic velocity of the flow, the single relaxation time , and the lattice spacing. The analytic solutions are the exact representation of these two flows without any approximation. Using the analytical solution, it is shown that in Poiseuille flow the bounce-back boundary condition introduces an error of first order in the lattice spacing. The boundary condition used by Kadanoffet al. in lattice gas automata to simulate Poiseuille flow is also considered for the triangular lattice Boltzmann BGK model. An analytical solution is obtained and used to show that the boundary condition introduces an error of second order in the lattice spacing. 相似文献
86.
High-purity Fe powder was mechanically milled under argon at ambient temperature using an SPEX 8000 mill. The local atomic and magnetic structure was studied using57Co/Fe Mössbauer and111In/Cd perturbed angular correlations (PAC) spectroscopies. After 32 hours of milling, X-ray diffraction revealed effective grain diameters of 18 nm and energy-dispersive X-ray analysis indicated a Cr impurity concentration of 5%, presumably introduced by mechanical attrition of steel ball bearings used for milling. In addition to a spectral component very similar to bulk iron metal, the Mössbauer spectra exhibited hyperfine field shifts attributed to the Cr impurities. PAC spectra on Fe milled for 5 h, with no contamination, exhibited two components: (1) A slightly broadened magnetic interaction attributed to interior, defect-free sites of In/Cd probes with a mean hyperfine field slightly greater than in macroscopic grains. The defect-free site fraction grew appreciably during milling, even though In is essentially insoluble in Fe. (2) An indistinct signal due to mixed magnetic and quadrupole interactions attributed to probes at surface or other defect sites. 相似文献
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The sequence of beta-lithiation and electrophilic substitution of beta-aryl secondary amides is reported. The lithiations occur regioselectively at the beta-position, and the resulting lithiated intermediates can be reacted with a wide range of electrophiles to give substituted products. Reactions of beta-lithiated amides bearing an alpha-substituent provide substituted products with high diastereoselectivity. Electrophilic substitutions of beta-lithiated N-methylamides in the presence of the chiral diamine (-)-sparteine provide highly enantioenriched products. The methodology is used to synthesize enantioenriched beta-aryl beta-substituted amides, acids, and lactones. 相似文献