Synthesis of heterocyclic compounds via nucleophilic aroylation catalyzed by imidazolidenyl carbene

Xanthones and acridones were synthesized from 3,4-difluoronitrobenzene and 2-fluorobenzaldehydes in two or three steps. The key step was nucleophilic aroylation catalyzed by imidazolidenyl carbene. The nucleophilic aroylation of 3,4-difluoronitrobenzene afforded 2,2'-difluoro-4-nitrobenzophenones. The cyclization of the difluorobenzophenones with O-nucleophile and N-nucleophile yielded 3-nitroxanthones and 3-nitroacridones, respectively. Indazole, quinolino[2,3-b]quinoxaline, and thianaphtho[2,3-b]quinoxaline derivatives were also synthesized via nucleophilic aroylation of 2,3-dichloroquinoxaline followed by cyclization with nucleophiles.     

Stereo structure-controlled and electronic structure-controlled estrogen-like chemicals to design and develop non-estrogenic bisphenol A analogs based on chemical hardness concept

The aim of this study was to elucidate the structure-activity relationship of bisphenol A (BPA) analogs using absolute hardness (eta) and absolute electronegativity (chi) (chemical hardness) and to design a non-estrogen active BPA. To determine the structure-activity relationships of BPA analogs, we investigated MCF-7 cell proliferation stimulated by BPA analogs and an eta-chi diagram based on the electronic structure of the BPA analogs. The results show that the actions of the environmental hormones BPA analogs have two chemical properties; (i) 'stereo structure-controlled' and (ii) 'electronic structure-controlled' estrogen-like chemical activities. Therefore, we designed and synthesized BPA analogs which do not possess these 2 characteristics, ((i) and (ii)), and demonstrate the non-estrogen activity of the analog.     

Assisting the diagnosis of thyroid diseases with Bayesian-type and SOM-type neural networks making use of routine test data

Patients with hyperthyroidism sometimes take much time to receive the final diagnosis. To improve patient QOL, simple screening for hyperthyroidism by thyroid non-specialists at the physical check-up is highly expected. Therefore, we applied both Bayesian-type and SOM-type neural networks since we assured the approach useful in analysing thyroid function diagnosis in the previous work. Routine test (14 parameters) data from 66 subjects with a known diagnosis (18 patients with hyperthyroidism and 48 healthy volunteers) were adopted as learning data, and then 142 individuals who also received the same routine tests at the Tohoku University Hospital were screened to predict patients with hyperthyroidism. Both neural networks using 14 parameters predicted several patients as having hyperthyroidism with high probability, including all three hyperthyroid patients diagnosed later by the physician. Further detailed analysis of the routine test parameters that were important for classification found that screening with a set of three parameters (alkaline phosphatase, serum creatinine and total cholesterol) or plus aspartate aminotransferase allowed for quite accurate screening. These results showed that the same neural networks as previous work allows simple screening of patients for hyperthyroidism on the basis of routine test data, and that physicians not specializing in the thyroid can rapidly identify individuals suspected of having hyperthyroidism, to permit a rapid referral for examination and treatment by thyroid specialists.     

(tBu2MeSi)2Sn=Sn(SiMetBu2)2: a distannene with a >Sn=Sn< double bond that is stable both in the solid state and in solution

((t)Bu(2)MeSi)(2)Sn=Sn(SiMe(t)Bu(2))(2) 1, prepared by the reaction of (t)Bu(2)MeSiNa with SnCl(2)-diox in THF and isolated as dark-green crystals, represents the first example of acyclic distannene with a Sn=Sn double bond that is stable both in the crystalline form and in solution. This was proved by the crystal and NMR spectral data of 1. Distannene 1 has these peculiar structural features: a shortest among all acyclic distannenes Sn=Sn double bond of 2.6683(10) A, a nearly planar geometry around both Sn atoms, and a highly twisted Sn=Sn double bond. The reactions of 1 toward carbon tetrachloride and phenylacetylene also correspond to the reactivity anticipated for the Sn=Sn double bond. The one-electron reduction of 1 with potassium produced the distannene anion radical, the heavy analogue of alkene ion radicals, for which the particular crystal structure and low-temperature EPR behavior are also discussed.     

Symmetrized correlation function for liquid para-hydrogen using complex-time pair-product propagators

We present a simple and efficient method for calculating symmetrized time correlation functions of neat quantum fluids. Using the pair-product approximation to each complex-time quantum mechanical propagator, symmetrized correlation functions are written in terms of a double integral for each degree of freedom with a purely positive integrand. At moderate temperatures and densities, where the pair-product approximation to the Boltzmann operator is sufficiently accurate, the method leads to quantitative results for the early time part of the correlation function. The method is tested extensively on liquid para-hydrogen at 25 K and used to obtain accurate quantum mechanical results for the initial 0.2 ps segment of the symmetrized velocity autocorrelation function of this system, as well as the incoherent dynamic structure factor at certain momentum transfer values.     

Nonlinear effects on solvation dynamics in simple mixtures

The authors applied the time dependent density functional method (TDDFM) and a linear model to solvation dynamics in simple binary solvents. Changing the solute-solvent interactions at t=0, the authors calculated the time evolution of density fields for solvent particles after the change (t>0) by the TDDFM and linear model. First, the authors changed the interaction of only one component of solvents. In this case, the TDDFM showed that the solvation time decreased monotonically with a mole fraction of the solvent strongly interacting with the solute. The monotonical decreases agreed with experimental results, while the linear model did not reproduce these results. The authors also calculated the solvation time by changing the interaction of both components. The calculation showed that the mole fraction dependence had the peak. The TDDFM presented a much higher peak than the linear model. The difference between the TDDFM and the linear model was caused by a nonlinear effect on an exchange process of solvent particles.     

Co2(CO)8-catalyzed intramolecular hetero-Pauson-Khand reaction of alkynecarbodiimide: synthesis of (+/-)-physostigmine

[reaction: see text] Herein we describe a novel Co(2)(CO)(8)-catalyzed intramolecular aza-Pauson-Khand-type reaction of alkynecarbodiimide derivatives affords pyrrolo[2,3-b]indol-2-one ring systems in reasonable yields. This is the first reported Co(2)(CO)(8) successfully applied in the hetero-Pauson-Khand reaction. Significantly, the transformation of one of our pyrrolo[2,3-b]indol-2-one derivatives into the indole alkaloid, (+/-)-physostigmine, was completed in a highly stereoselective manner.     

Electron conductive three-dimensional polymer of cuboidal C60

Single crystals of three-dimensional (3D) C60 polymer were prepared by the topotactic conversion of two-dimensional (2D) C60 polymer single crystals at a pressure of 15 GPa at 600 degrees C. The x-ray single crystal study revealed that the 3D C60 polymer crystallized in a body centered orthorhombic space group Immm, and spherical C60 monomer units were substantially deformed to rectangular parallelepiped (cuboidal) shapes, each unit being bonded to eight cuboidal C60 neighbors via [3 + 3] cycloaddition. The 3D C60 polymer was electron conductive, in contrast with the nonconductive behavior of 2D polymers.     

Supernova neutrino nucleosynthesis of light elements with neutrino oscillations

Light element synthesis in supernovae through neutrino-nucleus interactions, i.e., the v process, is affected by neutrino oscillations in the supernova environment. There is a resonance of 13-mixing in the O/C layer, which increases the rates of charged-current -process reactions in the outer He-rich layer. The yields of 7Li and 11B increase by about a factor of 1.9 and 1.3, respectively, for a normal mass hierarchy and an adiabatic 13-mixing resonance, compared to those without neutrino oscillations. In the case of an inverted mass hierarchy and a nonadiabatic 13-mixing resonance, the increase in the 7Li and 11B yields is much smaller. Observations of the 7Li/11B ratio in stars showing signs of supernova enrichment could thus provide a unique test of neutrino oscillations and constrain their parameters and the mass hierarchy.     

On the cohomology of free and twisted loop spaces

A natural extension of the cohomology suspension to a free loop space is constructed from the evaluation map and is shown to have good properties in cohomology calculation. This map is generalized to a twisted loop space which is a space of paths twisted by a given self-map of the underlying space. As an application, the cohomology of free and twisted loop spaces of classifying spaces of compact Lie groups, including some finite Chevalley groups, is calculated.