The Diels–Alder reactions of quinone imine ketals

2004 ◽  
Vol 82 (2) ◽  
pp. 131-138 ◽  
Author(s):  
Scott C Banfield ◽  
Michael A Kerr
Keyword(s):  
High Pressures ◽  
Ambient Pressure ◽  
Quinone Imine ◽  
Diels Alder

N-Benzoyl- and N-arylsulfonyl-p-benzoquinone-mono-imine ketals (QIKs) undergo smooth Diels–Alder cycloadditions with typical 1,3-butadienes to yield the expected endo adducts. Treatment with catalytic acid rapidly converts the adducts to dihydronaphthalenes. The N-benzoyl derivatives require high pressures for cycloadditions while the N-tosyl and N-nosyl derivatives proceed under thermal (ambient pressure) conditions. In all cases the cycloadditions are completely regioselective.Key words: Diels–Alder, quinone imine ketal, hyperbaric chemistry.

Molecular Dynamics Simulations on Melting of Aluminum

2013 ◽  
Vol 423-426 ◽  
pp. 935-938 ◽  
Author(s):  
Ji Feng Li ◽  
Xiao Ping Zhao ◽  
Jian Liu
Keyword(s):  
Molecular Dynamics ◽  
Melting Point ◽  
Molecular Dynamics Simulations ◽  
High Pressures ◽  
Ambient Pressure ◽  
Initial Porosity ◽  
Equilibrium Melting Point ◽  
Porosity Effect ◽  
Dynamics Simulations ◽  
Experimental Melting Point

Molecular dynamics simulations were performed to calculate the melting points of perfect crystalline aluminum to high pressures. Under ambientpressure, there exhibits about 20% superheating before melting compared to the experimental melting point. Under high pressures, thecalculated melting temperature increases with the pressure but at a decreasing rate, which agrees well with the Simon's melting equation. Porosity effect was also studied for aluminum crystals with various initial porosity at ambient pressure, which shows that the equilibrium melting point decreases with the initial porosity as experiments expect.

scholarly journals Pressure-Dependent Clustering in Ionic-Liquid-Poly (Vinylidene Fluoride) Mixtures: An Infrared Spectroscopic Study

Nanomaterials ◽  
2021 ◽  
Vol 11 (8) ◽  
pp. 2099
Author(s):  
Teng-Hui Wang ◽  
Wei-Xiang Wang ◽  
Hai-Chou Chang
Keyword(s):  
High Pressure ◽  
High Pressures ◽  
Vinylidene Fluoride ◽  
Ambient Pressure ◽  
Infrared Spectroscopic Study ◽  
Research Attention ◽  
Nanoscale Structures ◽  
Local Structures ◽  
Poly Vinylidene Fluoride ◽  
Hydrogen Bonded

The nanostructures of ionic liquids (ILs) have been the focus of considerable research attention in recent years. Nevertheless, the nanoscale structures of ILs in the presence of polymers have not been described in detail at present. In this study, nanostructures of ILs disturbed by poly(vinylidene fluoride) (PVdF) were investigated via high-pressure infrared spectra. For 1-(2-hydroxyethyl)-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([HEMIm][TFSI])-PVdF mixtures, non-monotonic frequency shifts of the C4,5-H vibrations upon dilution were observed under ambient pressure. The experimental results suggest the presence of microheterogeneity in the [HEMIm][TFSI] systems. Upon compression, PVdF further influenced the local structure of C4,5–H via pressure-enhanced IL–PVdF interactions; however, the local structures of C2–H and hydrogen-bonded O–H were not affected by PVdF under high pressures. For choline [TFSI]–PVdF mixtures, PVdF may disturb the local structures of hydrogen-bonded O–H. In the absence of the C4,5–H⋯anion and C2–H⋯anion in choline [TFSI]–PVdF mixtures, the O–H group becomes a favorable moiety for pressure-enhanced IL–PVdF interactions. Our results indicate the potential of high-pressure application for designing pressure-dependent electronic switches based on the possible changes in the microheterogeneity and electrical conductivity in IL-PVdF systems under various pressures.

The concentration and pressure dependent diffusion of carbon dioxide in nitrile rubbers

1992 ◽  
Vol 339 (1655) ◽  
pp. 497-519 ◽  
Keyword(s):  
Carbon Dioxide ◽  
Diffusion Coefficient ◽  
High Pressures ◽  
Ambient Pressure ◽  
Weight Fraction ◽  
Gas Pressure ◽  
Time Dependent ◽  
Initial Increase ◽  
Parametric Function ◽  
Ambient Gas

The paper reports the results of an experimental and associated analytical study of the time dependent adsorption of carbon dioxide gas into two nitrile elastomers. The mass gas sorption has been measured using a device based on a vibrating reed to a weight fraction accuracy of ca . 0.05 % at 47 °C in the ambient gas pressure range 0.1-34 MPa. The experimental method is described and data are provided. These data are used to compute the most effective description of the diffusion process by invoking a number of different diffusion coefficient, D(θ), characteristics, where θ denotes lapsed time, ambient pressure and local ambient gas concentration within the elastomers. The numerical procedures adopted to perform the fitting of the experimental data with various D(θ) characteristics are described and the quality of the fit is assessed. The D(θ) characteristics chosen have no particular physical basis but follow established empirical precedents. The characteristics of the parameters associated with the various D(θ) functions generally indicate that as the gas is embibed with progressively increasing ambient pressures the diffusion coefficient increases. At high pressures the diffusion is arrested and the coefficient decreases. We have associated the initial increase with gas induced plasticization and the eventual decreases with the effect of the hydrostatic component of the ambient gas pressure. The parameter fitting also indicates that the diffusion is arrested with lapsed time which is tentatively associated with time dependent volumetric relaxations. These interpretations apart, the data and analyses clearly indicate that the transport is not simply fickian and a relatively complex parametric function to describe the sensitivity of the diffusion coefficient to time, concentration and pressure is necessary for these systems.

PRESSURE-INDUCED ELECTRONIC PHASE TRANSITIONS AND SUPERCONDUCTIVITY IN TITANIUM

2009 ◽  
Vol 23 (05) ◽  
pp. 723-741 ◽  
Author(s):  
K. IYAKUTTI ◽  
C. NIRMALA LOUIS ◽  
S. ANURATHA ◽  
S. MAHALAKSHMI
Keyword(s):  
High Pressure ◽  
Band Structure ◽  
Fermi Surface ◽  
High Pressures ◽  
Ambient Pressure ◽  
Structural Phase ◽  
Normal Pressure ◽  
Orbital Method ◽  
Superconducting Transition ◽  
Electronic Band

The electronic band structure, density of states, structural phase transition, superconducting transition and Fermi surface cross section of titanium ( Ti ) under normal and high pressures are reported. The high pressure band structure exhibits significant deviations from the normal pressure band structure due to s → d transition. On the basis of band structure and total energy results obtained using tight-binding linear muffin-tin orbital method (TB LMTO), we predict a phase transformation sequence of α( hcp ) → ω (hexagonal) → γ (distorted hcp) → β (bcc) in titanium under pressure. From our analysis, we predict a δ (distorted bcc) phase which is not stable at any high pressures. At ambient pressure, the superconducting transition occurs at 0.354 K. When the pressure is increased, it is predicted that, Tc increases at a rate of 3.123 K/Mbar in hcp–Ti . On further increase of pressure, Tc begins to decrease at a rate of 1.464 K/Mbar. The highest value of Tc(P) estimated is 5.043 K for hcp–Ti , 4.538 K for ω– Ti and 4.85 K for bcc – Ti . From this, it is inferred that the maximum value of Tc(P) is rather insensitive to the crystal structure of Ti . The nonlinearities in Tc(P) is explained by considering the destruction and creation of new parts of Fermi surface at high pressure. At normal pressure, the hardness of Ti is in the following order: ω- Ti > hcp - Ti > bcc- Ti > γ- Ti .

The Diels—Alder Reactions of Quinone Imine Ketals.

ChemInform ◽  
2004 ◽  
Vol 35 (33) ◽  
Author(s):  
Scott C. Banfield ◽  
Michael A. Kerr
Keyword(s):  
Quinone Imine ◽  
Diels Alder

LEAD-CHALCOGENIDES UNDER PRESSURE: AB-INITIO STUDY

2013 ◽  
Vol 22 ◽  
pp. 612-618 ◽  
Author(s):  
DINESH C. GUPTA ◽  
IDRIS HAMID
Keyword(s):  
Phase Transition ◽  
High Pressure ◽  
Ab Initio ◽  
Band Gap ◽  
Rock Salt ◽  
High Pressures ◽  
Ambient Pressure ◽  
High Pressure Phase ◽  
Lead Chalcogenides ◽  
Pressure Phase

ab-initio calculations using fully relativistic pseudo-potential have been performed to investigate the high pressure phase transition, elastic and electronic properties of lead-chalcogenides including the less known lead polonium. The calculated ground state parameters, for the rock-salt structure show good agreement with the experimental data. The enthalpy calculations show that these materials undergo a first-order phase transition from rock-salt to CsCl structure at 19.4, 15.5, 11.5 and 7.3 GPa for PbS, PbSe, PbTe and PbPo, respectively. Present calculations successfully predicted the location of the band gap at L-point of Brillouin zone as well as the value of the band gap in every case at ambient pressure. It is observed that unlike other lead-chalcogenides, PbPo is semi-metal at ambient pressure. The pressure variation of the energy gap indicates that these materials metalized under high pressures. For this purpose, the electronic structure of these materials has also been computed in parent as well as in high pressure phase.

ChemInform Abstract: The Diels-Alder Reactions of Quinone Imine Ketals: A Synthesis of the Ergot Skeleton.

ChemInform ◽  
2010 ◽  
Vol 32 (28) ◽  
pp. no-no
Author(s):  
Scott C. Banfield ◽  
Michael A. Kerr
Keyword(s):  
Quinone Imine ◽  
Diels Alder

High-pressure transformations of NbO2F

2000 ◽  
Vol 56 (2) ◽  
pp. 189-196 ◽  
Author(s):  
Stefan Carlson ◽  
Ann-Kristin Larsson ◽  
Franziska E. Rohrer
Keyword(s):  
Phase Transition ◽  
High Pressure ◽  
High Pressures ◽  
Ambient Pressure ◽  
Close Packing ◽  
Hexagonal Close Packing ◽  
Rietveld Refinements ◽  
X Ray ◽  
Anion Coordination ◽  
Diamond Anvil

The ReO3-type structure NbO2F, niobium dioxyfluoride, has been studied at high pressures using diamond anvil cells and synchrotron X-ray radiation. High-pressure powder diffraction measurements have been performed up to 40.1 GPa. A phase transition from the cubic (Pm3¯m) ambient pressure structure to a rhombohedral (R3¯c) structure at 0.47 GPa has been observed. Rietveld refinements at 1.38, 1.96, 3.20, 6.23, 9.00 and 10.5 GPa showed that the transition involves an a − a − a − tilting of the cation–anion coordination octahedra and a change of the anion–anion arrangement to approach hexagonal close packing. Compression and distortion of the Nb(O/F)6 octahedra is also revealed by the Rietveld refinements. At 17–18 GPa, the diffraction pattern disappears and the structure becomes X-ray amorphous.

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