o-Phenylene halocarbenonitrenes and o-phenylene chlorocarbenocarbene: a combined experimental and computational approach

[reaction: see text] Computations find that o-phenylene(halo)carbenonitrenes 2-XN, X = F, Cl, Br, have quinoidal singlet biradical ground states such as the parent o-phenylenecarbenonitrene (2-HN). Compared to the parent 2-HN, halogen substitution stabilizes the A' states relative to the A' ones. Halogen substitution also affects the barrier and exothermicity of the ring-opening reaction (to form unsaturated nitriles 4-XN, X = F, Cl, Br), but it has a smaller effect on the ring-closing reaction (to form benzo(aza)cyclobutadiene 3-XN, X = F, Cl, Br). Attempts to generate and observe the o-phenylene(halo)carbenonitrenes 2-XN, X = F, Cl, Br, using matrix isolation spectroscopy under conditions similar to those of the successful observation of 2-HN failed. Instead, the observed photoproducts were a mixture of 3-XN and 4-XN. In each case, the major product of the mixture appears to be the thermodynamically more stable one. In the case of X = Br, the observed mixture contains an additional component that is postulated to be Z-6-BrN. o-Phenylenechlorocarbenocarbene is also computed to have a quinoidal singlet biradical ground state and relatively stabilized A' excited states. Attempts to generate the biscarbene under matrix isolation conditions led to the detection of benzochlorocyclobutadiene (3-ClC), small amounts of the ring-open product (dienediyne 4-ClC), and cycloalkyne 5-ClC. Computations suggest that the formation of 5-ClC implies the generation of Z-6-ClC, which is analogous to the formation of Z-6-BrN from 2-BrN.     

Novel [2 + 2] photocycloaddition-induced rearrangement of bichromophoric naphthalene-tethered resorcinol ethers

The first examples of sequential photocycloaddition-rearrangement reactions of naphthalene-tethered resorcinol ethers are described. Bichromophoric aromatic compounds with naphthalene and resorcinol ether moieties were irradiated in the presence/absence of a small amount of acid to give the corresponding cycloaddition-rearrangement products. From the determination of quantum yields, steady-state fluorescence spectral studies, and fluorescence lifetime measurements, the mechanism of this novel photoinduced multistep reaction was elucidated to involve the initial intramolecular exciplex formation, followed by the intramolecular [2 + 2] photocycloaddition between the two aromatic rings and the subsequent acid-catalyzed skeletal rearrangement of the resulting cyclobutane derivative leading to the final products.     

Substituent effects on the tautomer ratios between the hydrazone imine and diazenyl enamine forms in side-chained quinoxalines

The 3-(arylhydrazono)methyl-2-oxo-1,2-dihydroquinoxalines 9–11 were synthesized by the reaction of the quinoxalines 6–8 with various p-substituted benzenediazonium salts. Compounds 9–11 showed the tautomeric equilibria between the hydrazone imine A and diazenyl enamine B forms in dimethyl sulfoxide media. The substituent effect on the tautomer ratios of A to B was studied by the nmr spectroscopy to clarify that the presence of the ester group R² on the hydrazone carbon and electron-donating p-substituent R¹ on the side chain benzene ring exhibited a tendency to increase the ratios of the tautomer A .     

Selective binding of steroids by 2,2'-biquinoline-4,4'-dicarboxamide-bridged bis(beta-cyclodextrin): fluorescence enhancement by guest inclusion

A novel bis(beta-cyclodextrin) was synthesized, and its binding behavior with steroids was investigated to demonstrate that the cooperative co-inclusion of guest and tether by two cyclodextrin moieties is operative to afford the highest molecular selectivity of up to 3.6 for deoxycholate over taurocholate.     

Di(triptycyl)carbene: a fairly persistent triplet dialkylcarbene

The title carbene was generated and characterized by matrix spectroscopy (ESR and UV/vis) and laser flash photolysis along with theoretical calculations, which revealed interesting effects of triptycyl groups on structure and reactivities of carbenes.     

Supramolecular chirogenesis in zinc porphyrins: equilibria, binding properties, and thermodynamics

Complexation mechanism, binding properties and thermodynamic parameters of supramolecular chirality induction in the achiral host molecule, syn (face-to-face conformation) ethane-bridged bis(zinc porphyrin), upon interaction with chiral monoamine and monoalcohol guests have been studied by means of the UV-vis, CD, (1)H NMR, and ESI MS techniques. It was found that the chirogenesis process includes three major equilibria steps: the first guest ligation to a zinc porphyrin subunit of the host (K(1)), syn to anti conformational switching (K(S)), and further ligation by a second guest molecule to the remaining ligand-free zinc porphyrin subunit (K(2)), thus forming the final bis-ligated species possessing supramolecular chirality. The validity of this equilibria model is confirmed by the excellent match between the calculated and experimentally observed spectral parameters of the bis-ligated species. The second ligation proceeds in a cooperative manner as K(2) > K(1) for all supramolecular systems studied, regardless of the structure of the chiral ligand used. The binding properties are highly dependent on the nature of the functional group (amines are stronger binders than alcohols) and on the structure of the chiral guests (primary and aliphatic amines have overall binding constant values greater than those of secondary and aromatic amines, respectively).     

Succession of stacking disorder in hard-sphere crystal under gravity by Monte Carlo simulation

We have performed Monte Carlo simulations of hard spheres under gravity. Vertical boundaries are hard walls, which are well separated with each other. On the other hand, the periodic boundary condition is imposed in the horizontal direction. While we previously reported enhancement of crystallinity as well as crystallization due to gravity, we present here the results that demonstrate the succession of a defect. In case that the crystal formed at the bottom of the system includes kinds of stacking disorders for the (0 0 1) growth, twin band structure develops as mediated by a stacking disorder succeeded in the crystal formed in the fluid region which lies on the bottom crystal. In case that the stacking structure along horizontal direction changes from the (1 1 1) stacking to the (0 0 1) stacking, twin band structure in the (0 0 1) stacking region develops as succeeded in the crystal transformed. The twin band structure also becomes large with its upward growth.     

Uptake of alkali and alkaline earth metal ions into electrochemically pretreated glassy carbon fibres by flow-through electrolysis

When glassy carbon fibres are used, alkali and alkaline earth metal ions are adsorbed in the micropores which are created or activated by oxidative treatment of the fibres. The average pore radius was estimated to be 2 nm by nitrogen adsorption experiments. Uptake was studied with a flow system consisting of a flow-through carbon-fibre electrode; a dropping mercury electrode at the end of the flow line monitored changes in the metal ion concentrations. The ions were taken up at negative potentials and released at positive potentials. The amount taken up increased in the sequence Na⁺ < Li⁺ < H⁺, suggesting that the ions were desolvated before entering the pore system.     

Quinolone analogues 6 [1‐5]. Synthesis of 3‐halogeno‐1‐methylpyridazino[3,4‐b]quinoxalin‐4(1H)‐ones

The reaction of the quinoxaline N‐oxides 7a,b with diethyl ethoxymethylenemalonate gave the 1‐methylpyridazino[3,4‐b]quinoxaline‐4,4‐dicarboxylates 8a,b , whose reaction with N‐bromosuccinimide or N‐chlorosuccinimide afforded the 3‐halogeno‐1‐methylpyridazino[3,4‐b]quinoxaline‐4,4‐dicarboxylates 9a‐d. The reaction of compounds 9a‐d with hydrazine hydrate resulted in hydrolysis and decarboxylation to provide the 3‐halogeno‐1‐methylpyridazino[3,4‐b]quinoxaline‐4‐carboxylates 10a‐d , whose reaction with nitrous acid effected oxidation to furnish the 3‐halogeno‐4‐hydroxy‐1‐methylpyridazino[3,4‐b]quinoxaline‐4‐carboxylates 11a‐d , respectively. The reaction of compounds 11a‐d with hydrazine hydrate afforded the 3‐halogeno‐1‐methylpyridazino[3,4‐b]quinoxalin‐4‐ols 12a‐d , whose oxidation provided the 3‐halogeno‐1‐methylpyridazino[3,4‐b]quinoxalin‐4(1H)‐ones 6a‐d , respectively. Compounds 6a‐d had antifungal activities in vitro.