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61.
The 13C and proton NMR spectra of six porphyrins bearing the substituent orientation characteristic of the natural “Type-IX” arrangement are reported and assigned. Significant concentration effects in the spectra of the free base porphyrins, together with the broadening of the Cα (and occasionally Cβ) carbon resonances due to NH tautomerism caused a significant loss of data in these spectra. However, the spectra of the corresponding zinc(II) porphyrins (with addition of excess pyrrolidine) show that both these extraneous effects are completely removed to give well-resolved spectra with accurately reproducible chemical shifts. These spectra are assigned and an analysis of the chemical shifts allows the deduction of substituent chemical shift (SCS) parameters for the peripheral substituents at the beta and meso carbons. There is no global effect of these beta substituents, the beta carbon SCS being confined to the immediate pyrrole ring, and the meso carbon SCS to the two adjacent pyrrole rings. The SCS parameters are analyzed and it is shown how they can be used to predict the peripheral and meso carbon chemical shifts of any porphyrin bearing the substituents discussed. 相似文献
62.
63.
Espy MA Dehnhard D Edwards CM Palarczyk M Langenbrunner JL Davis B Burleson GR Blanchard S Gibbs WR Lail B Nelson B Park BK Zhao Q Cummings WJ Delheij PP Jennings BK Henderson R Häusser O Thiessen D Brash E Jones MK Larson B Brinkmöller B Maeda K Morris CL O'Donnell JM Penttilä S Swenson D Tupa D Bennhold C Kamalov SS 《Physical review letters》1996,76(20):3667-3670
64.
We show for the first time that a classical Hookean viscoelastic constitutive law for rubbery materials can predict the impact forces and deflections measured with a commercial drop tester when a mass, or tup with a flat impacting surface is dropped onto a flat pad of commercial impact-absorbing rubber. The viscoelastic properties of the rubber, namely the relaxation times and strengths, are obtained by a standard rheological linear-oscillatory test, and the equation of momentum transfer is then solved, using these measured parameters, assuming a uniaxial deflection of the pad during the impact. Good agreement between measured and predicted forces and deflections is obtained for a series of various drop heights, tup masses, impact areas, and pad thicknesses, as long as the deflection of the pad relative to its thickness is small or modest (<50% or so), and as long as the area of the pad is less than or equal to that of the tup. When the pad area is greater than the tup, forces are higher than predicted, unless an empirical factor is introduced to account for the nonuniaxial stretching of the ring of material that extends outside of the impact area. These results imply that the impact-absorbing properties of a rubbery polymeric material can be assessed by simply examining the material's linear viscoelastic spectrum. 相似文献
65.
66.
Chromium-Reformatsky and chromium-homoaldol reactions run under neutral and mild reaction conditions. They are highly chemoselective, tolerant towards most common functional groups, and are not prone to retroaldol reactions. Initial studies directed to transfer these homogeneous chromium-mediated solution-phase reactions to solid phase are presented. The main objective was to develop a methodology to aid a combinatorial iterative strategy to polyols (polyketides) on solid phase. A general reactivity problem was observed with polystyrene based resins compared to the solution-phase reactions, independent if the electrophilic (aldehyde) or nucleophilic (bromide) end of the polyol chain was supported to the resin. A complicated penetration, or loss of the polar solvent environment after penetration into the resin, might be responsible for the reduced reactivity. Application of either a soluble polystyrene resin or a polystyrene resin with a polar polyethylene glycol tether resulted in improved yields. 相似文献
67.
Harry L. Yale 《Journal of heterocyclic chemistry》1971,8(2):205-208
A number of arylamidoximes, an o-aminobenzaloxime, and an o-aminobenzenesulfonamide have been reacted with boronic acids to give three novel boron containing heterocycles. Evidence, based on mass spectroscopy, that the product from o-aminobenzaloxime is a 1,2-dihydro-l,3,2-benzodiazaborine 3-oxide, is presented. 相似文献
68.
69.
Frampton MJ Akdas H Cowley AR Rogers JE Slagle JE Fleitz PA Drobizhev M Rebane A Anderson HL 《Organic letters》2005,7(24):5365-5368
[structure: see text] A vinylene-linked porphyrin dimer, with no substituents at the beta-positions, has been synthesized by CuI/CsF promoted Stille coupling. In the crystal structure of this dimer, the C(2)H(2) bridge is twisted by 45 degrees relative to the plane of the porphyrins. The absorption, emission spectra, and electrochemistry reveal substantial porphyrin-porphyrin pi-conjugation. The triplet excited-state absorption spectrum of this dimer makes it suitable for reverse saturable absorption at 710-900 nm. 相似文献
70.
Gianfranco Denti Mauro Ghedini Jon A. McCleverty Harry Adams Neil A. Bailey 《Transition Metal Chemistry》1982,7(4):222-224
Summary Treatment of [Mo{HB(3,5-Me2C3HN2)3}(NO)I2] with one or two moles of AgPF6 in acetonitrile afforded the paramagnetic (one unpaired electron) complex [Mo{HB(3,5-Me2C3NH2)3}(NO)(NCMe)2][PF6]. The structure of this complex was determined crystallographically, and the six-coordinate geometry of the complex cation confirmed. 相似文献