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101.
Suzanne Gelin Bernard Chantegrel Christian Deshayes 《Journal of heterocyclic chemistry》1982,19(5):989-991
The synthesis and biological activities of some 4-oxo-1-or-2-substituted 1H-or-2H-pyrano[4,3-c]pyrazole derivatives are described. 相似文献
102.
2-Arylidene-3-oxo-2,3,4,5,6,7-hexahydrobenzo[b]furans 2 react with hydrazine hydrate to afford 5,6,7,8-tetrahydro-4-cinnolones. By methylation, these compounds gave the corresponding N-1 and N-2 methyl derivatives. The mesoionic compounds are obtained, accompanied by 3-arylacetyl-4,5,6,7-tetrahydroindazoles upon reaction of 2 with methylhydrazine. 相似文献
103.
Lucas S Ferry D Demirdjian B Suzanne J 《The journal of physical chemistry. B》2005,109(38):18103-18106
We present an experimental work devoted to study of the thermodynamical properties of solid methanol. We combine Fourier transform infrared spectroscopy (FTIR) and mass spectrometry (MS) to measure, for the first time, the vapor pressure of various methanol solid phases and determine their Clausius-Clapeyron equations. We perform our experiments between T = 130 K and the triple point temperature T(t) = 175.61 K. When methanol is condensed from its vapor below T(t), we observe three different solid phases depending on temperature. A condensation at T = 130 K forms a metastable phase with an enthalpy of sublimation deltaH(metastable-vapor) = 42.9 +/- 0.5 kJ.mol(-1). Upon heating, this phase transforms itself at T approximately 145 K to the alpha-phase that has an enthalpy of sublimation deltaH(alpha-vapor) = 46.9 +/- 0.2 kJ.mol(-1). Cooling the alpha-phase does not lead back to the metastable phase, whereas heating this alpha-phase leads to the beta-phase occurrence at T(alpha-beta) = 157.36 K. This latter one is stable until T(t) and has an enthalpy of sublimation deltaH(beta-vapor) = 44.2 +/- 0.5 kJ.mol(-1). 相似文献
104.
Frazier BA Bartholomew ER Wolczanski PT DeBeer S Santiago-Berrios M Abruña HD Lobkovsky EB Bart SC Mossin S Meyer K Cundari TR 《Inorganic chemistry》2011,50(24):12414-12436
A series of Werner complexes featuring the tridentate ligand smif, that is, 1,3-di-(2-pyridyl)-2-azaallyl, have been prepared. Syntheses of (smif)(2)M (1-M; M = Cr, Fe) were accomplished via treatment of M(NSiMe(3))(2)(THF)(n) (M = Cr, n = 2; Fe, n = 1) with 2 equiv of (smif)H (1,3-di-(2-pyridyl)-2-azapropene); ortho-methylated ((o)Mesmif)(2)Fe (2-Fe) and ((o)Me(2)smif)(2)Fe (3-Fe) were similarly prepared. Metatheses of MX(2) variants with 2 equiv of Li(smif) or Na(smif) generated 1-M (M = Cr, Mn, Fe, Co, Ni, Zn, Ru). Metathesis of VCl(3)(THF)(3) with 2 Li(smif) with a reducing equiv of Na/Hg present afforded 1-V, while 2 Na(smif) and IrCl(3)(THF)(3) in the presence of NaBPh(4) gave [(smif)(2)Ir]BPh(4) (1(+)-Ir). Electrochemical experiments led to the oxidation of 1-M (M = Cr, Mn, Co) by AgOTf to produce [(smif)(2)M]OTf (1(+)-M), and treatment of Rh(2)(O(2)CCF(3))(4) with 4 equiv Na(smif) and 2 AgOTf gave 1(+)-Rh. Characterizations by NMR, EPR, and UV-vis spectroscopies, SQUID magnetometry, X-ray crystallography, and DFT calculations are presented. Intraligand (IL) transitions derived from promotion of electrons from the unique CNC(nb) (nonbonding) orbitals of the smif backbone to ligand π*-type orbitals are intense (ε ≈ 10,000-60,000 M(-1)cm(-1)), dominate the UV-visible spectra, and give crystals a metallic-looking appearance. High energy K-edge spectroscopy was used to show that the smif in 1-Cr is redox noninnocent, and its electron configuration is best described as (smif(-))(smif(2-))Cr(III); an unusual S = 1 EPR spectrum (X-band) was obtained for 1-Cr. 相似文献
105.
The regioselective synthesis of new 3-alkenyl-1-phenylpyrazoles 4 from the reaction of phenylhydrazine with 2,3-dihydro-4H-pyran-4-ones 1 is described. 相似文献
106.
W. Ken Busfield Ian D. Jenkins Michael J. Monteiro 《Journal of polymer science. Part A, Polymer chemistry》1997,35(2):263-270
The radical trapping technique employing 1,1,3,3-tetramethyl-1,3-dihydro-1H-isoindol-2-yloxyl as a scavenger has been used to investigate the reaction of t-butoxyl radicals with mixtures of ethyl vinyl ether and methyl methacrylate. The range of identified products includes those from both addition and hydrogen abstraction with both monomers, head addition with ethyl vinyl ether, and some second monomer addition products. Relative rate constants have been obtained for various pairs of constituent reactions. t-Butoxyl radicals add to ethyl vinyl ether one to two times faster than to methyl methacrylate, depending on which monomer is in excess. The ratio is less than 1 in nonolefinic solvents and as high as 6 in t-butanol. This solvent effect is thought to be due to the radicals complexing to either methyl methacrylate or t-butanol (H-bonding), thereby increasing its electrophilic character. © 1997 John Wiley & Sons, Inc. 相似文献
107.
The synthesis of an air‐stable series of Pd0 complexes with unsymmetric bidentate N‐pyridine N‐heterocyclic carbene ligands has been described. The carbenes were generated by synthesis of the silver(I) complexes from the imidazolium salts, followed by transmetallation of the C‐N ligands to obtain the target electron‐rich zerovalent palladium compounds. The bidentate coordination behaviour of the ligands was confirmed by 1H, 13C NMR and X‐ray spectroscopy. The complexes are active precatalysts for the selective transfer semihydrogenation of alkynes to Z‐alkenes, with selectivities up to 99%. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
108.
Experimental Techniques - 相似文献
109.
110.
S.J. Jenkins 《Surface science》2010,604(19-20):1688-1693
The surfaces of hcp crystals can show a variety of structural features and classes of symmetry that differ markedly from those of simpler fcc or bcc crystals. The hcp-{213?1} surface, for example, can occur in four distinct stereomorphs, interconverted by a combination of mirror operations (linking degenerate enantiomorphically related surfaces) and/or the removal of the outermost atomic layer (linking non-degenerate diamorphically related surfaces). The strict pattern of degeneracy amongst these stereomorphs is analogous to that found for molecules with two chiral centres, and hence it is possible to view this system as doubly-chiral. Simple nearest-neighbour bond-counting arguments, however, suggest that for {213?1} even the diamorphically related cases should be near-degenerate, despite the fact that they differ in having either a notably short or notably long interlayer spacing between the outermost layers (ideal spacing ratio 1:5). In the present work, this counterintuitive result is confirmed at the level of density functional theory, both for the ideal and relaxed {213?1} surfaces of Co, Ru and Re. 相似文献