Chemistry of 4-alkylaryloxenium ion "precursors": sound and fury signifying something?

Quinol esters 2b, 2c, and 3b and sulfonamide 4c were investigated as possible precursors to 4-alkylaryloxenium ions, reactive intermediates that have not been previously detected. These compounds exhibit a variety of interesting reactions, but with one possible exception, they do not generate oxenium ions. The 4-isopropyl ester 2b predominantly undergoes ordinary acid- and base-catalyzed ester hydrolysis. The 4-tert-butyl ester 2c decomposes under both acidic and neutral conditions to generate tert-butanol and 1-acetyl-1,4-hydroquinone, 8, apparently by an SN1 mechanism. This is also a minor decomposition pathway for 2b, but the mechanism in that case is not likely to be SN1. Decomposition of 2c in the presence of N3- leads to formation of the explosive 2,3,5,6-tetraazido-1,4-benzoquinone, 14, produced by N3--induced hydrolysis of 8, followed by a series of oxidations and nucleophilic additions by N3-. No products suggestive of N3--trapping of an oxenium ion were detected. The 4-isopropyl dichloroacetic acid ester 3b reacts with N3- to generate the two adducts 2-azido-4-isopropylphenol, 5b, and 3-azido-4-isopropylphenol, 11b. Although 5b is the expected product of N3- trapping of the oxenium ion, kinetic analysis shows that it is produced by a kinetically bimolecular reaction of N3- with 3b. No oxenium ion is involved. The sulfonamide 4c predominantly undergoes a rearrangement reaction under acidic and neutral conditions, but a minor component of the reaction yields 4-tert-butylcresol, 17, and 2-azido-4-tert-butylphenol, 5c, in the presence of N3-. These products may indicate that 4c generates the oxenium ion 1c, but they are generated in very low yields (ca. 10%) so it is not possible to definitively conclude that 1c has been produced. If 1c has been generated, the N3--trapping data indicate that it is a very short-lived and reactive species in H2O. Comparisons with similarly reactive nitrenium ions indicate that the lifetime of 1c is ca. 20-200 ps if it is generated, so it must react by a preassociation process. Density functional theory calculations at the B3LYP/6-31G*//HF/6-31G* level coupled with kinetic correlations also indicate that the aqueous solution lifetimes of 1a-c are in the picosecond range.     

The unsteady flow generated by an oscillating wall with transpiration

In this work, an analytical solution for the fluid behavior over flat plates with impulsive and oscillating motions, starting from rest, and with wall transpiration, is presented. The classical solution of this problem is given by Panton [7] and is found to be an especial case of the solution here presented. The analytical solution is obtained without the use of any special transformations, such as Laplace or Fourier transforms. Instead, an extension of the variable separation technique is used together with similarity arguments. A non-dimensional number—the transpiration rate—is used to take into account the injection or suction of fluid at the wall. This parameter is shown to be of great influence on the proposed velocity solution.     

wave superconductivity: Analysis of the electronic Raman data of and other cuprates

After briefly recalling the d + s model valid for some anisotropic high T c superconductors, we present a theory of electronic Raman spectra in that model and then compare it with new experimental data obtained for an overdoped Y123 single crystal. The d + s model appears to describe satisfactorily the experimental results, indicating a possible doping dependence of the mixing ratio. We note that the Raman spectrum of the overdoped Bi2212 could also be accounted for by the d + s superconductivity model. The case of Hg1212 (or Hg1223) is reexamined. It appears that the spontaneous breakdown of d-wave symmetry may be rather universal in high T c cuprates. Received: 3 March 1998 / Accepted: 30 April 1998     

Synthesis of 2‐amino‐1,4‐dihydro‐4‐quinolinones and diaminomethylene meldrum's acids derivatives as potential potassium channel openers

Starting from 5‐bismethylthiomethylene Meldrum's acid, the synthesis of 5‐diaminomethylene Meldrum's acids and 2‐aminoquinolone derivatives, structurally related to potassium channels openers pinacidil and diazoxide, is described.     

Effect of Zn and Ni impurities on the quasiparticle renormalization of superconducting Bi-2212

The Cu substitution by Zn and Ni impurities and its influence on the mass renormalization effects in angle-resolved photoelectron spectra (ARPES) of Bi2Sr2CaCu2O8-delta is addressed. We show that the nonmagnetic Zn atoms have a much stronger effect in both the nodal and antinodal parts of the Brillouin zone than magnetic Ni. The observed changes are consistent with the behavior of the spin resonance mode as seen by inelastic neutron scattering in YBCO. This strongly suggests that the "peak-dip-hump" and the kink in ARPES on the one side and neutron resonance on the other are closely related features.