Reactivity of the ester group attached isoxazoline, benzisoxazole, and isoxazole: a facial preparation of 3-acyl-substituted these heterocycles

A facile preparation of 3-acyl-substituted isoxazolines, benzisoxazoles, and isoxazoles from the corresponding 3-carboxylate esters is described. The process, involving reaction of the ester derivative of 3-carboxylic acid substituted heterocycles with Grignard or alkynyl lithium reagents, leads to direct generation of the corresponding 3-acyl heterocycle. The presence of α-imino ester moieties in the heterocyclic substrates for the reactions is thought to be a key feature governing the nature of these transformations. The synthetic utility of the new methodology is demonstrated by its application in a two-step route for the preparation of novel linked bis-heterocycles.     

Synthesis of 7‐acetyloxy‐3,7‐dimethy1‐7,8‐dihydro‐6H‐isochromene‐6,8‐dione and its analogues

7‐Alkanoyloxy‐3,7‐dimefhyl‐7,8‐dihydro‐6H‐isochromene‐6,8‐diones 12‐15 were synthesized in 69‐16% yields from the reaction of 2,4‐dihydroxy‐3‐methyl‐6‐(2‐oxopropyl)benzaldehyde 11 with p‐toluenesulfonic acid in various carboxylic acids such as acetic acid, propionic acid, butyric acid and heptanoic acid followed by oxidation with lead tetraacetate. On the other hand, (±)‐daldinin A 5 (oleate) was not obtained using oleic acid as a medium. In the cases of heptanoic acid and oleic acid, esters 16 and 17 were produced in 23 and 9% yields, respectively. 6,8‐Dihydroxy‐3,7‐dimethyl‐2‐benzopyrylium p‐toluenesulfonate 31 is considered as the intermediate for the production of 12‐15. Overall yields of isochromenes 12‐15 were 26‐6% starting from 2‐methylresorcinol for seven steps.     

Crystal structure of methyl endo-8-cyano-exo-8-methyl-3-oxo-2-oxabicyclo[2.2.2]oct-5-ene-6-carboxylate.

A photochemical cycloaddition reaction of methyl 2-pyrone-5-carboxylate with methacrylonitrile mainly gave a [4 + 2] cycloadduct, assigned as methyl endo-8-cyano-exo-8-methyl-3-oxo-2-oxabicyclo[2.2.2]oct-5-ene-6-carboxylate, whose structure was determined by an X-ray diffraction study. The formation of the cycloadduct was reasonably explained by considering a biradical intermediate having a less steric hindrance between the methoxycarbonyl group and the cyano group.     

Cepaic acid, a novel yellow xanthylium pigment from the dried outer scales of the yellow onion Allium cepa

Cepaic acid was isolated as a novel xanthylium yellow pigment from the dried outer scales of the yellow onion Allium cepa Linne. Its structure was elucidated on the basis of ESI-MS and 2D NMR spectroscopy as a 9-carboxy-1,3,6,8-tetrahydroxyxanthylium, which suggests that cepaic acid and other yellow pigments in the dried outer skin of onion were formed by the nucleophilic reaction of phloroglucinol derived from quercetin, a flavonol in onion scales, by autoxidation to glyoxylic acid. To our knowledge, this is the first report of such a pigment in yellow onion.     

Preparation of poly(1,4-phenylene)s by electro-oxidative polymerization

The effect of substituents on the electropolymerization of benzene derivatives and the redox properrties of the corresponding polymers were determined using Brown's substituent constants (σ⁺). Electron-donating groups lower the oxidation potential by which increase in the current efficiency was observed. However, stabilization of the produced cation radicals by the electron-donating groups resulted in a decrease in the polymerization efficiency. The appropriate values of σ⁺ for the efficient polymerization ranged near ?1.5.     

Mesogenicity of testosterone and estrone derivatives

Mesogenicity of 3β, 17β-bis(4-n-alkoxybenzoyloxy) androstene homologues (BABA) (carbon No. of alkoxy group, n, = 1-10) were studied by use of D.S.C. and a polarized microscopy. It was found that the n = 4-10 compounds of BABA have one cholesteric mesophase with high thermal stability enantiotropically, and that the n = 1-3 compounds decompose just above the melting point. Mesogenicities of BABA and several testosterone and estrone derivatives were also discussed from the perspective of chemical structure and shape. The presence of an intramolecular long-range dipole coupling in two alkoxybenzoyloxy chromophores is found in BABA from CD spectral studies.     

Carbazole Dendrimers as Solution‐Processable Thermally Activated Delayed‐Fluorescence Materials

Recently, thermally activated delayed fluorescence (TADF) materials have received increasing attention as effective emitters for organic light‐emitting diodes (OLEDs). However, most of them are usually employed as dopants in a host material. In this report, carbazole dendrimers with a triphenyl‐s‐triazine core are reported, which are the first solution‐processable, non‐doped, high‐molecular‐weight TADF materials. The dendrimers were obtained by a new and facile synthetic route using the tert‐butyldimethylsilyl moiety as a protecting group. All dendrimers showed TADF in toluene. Measurements of the temperature‐dependent luminescence lifetime revealed that spin‐coated neat films also showed TADF with moderate quantum yields. OLED devices incorporating these dendrimers as spin‐coated emitting layers gave external quantum efficiencies of up to a 3.4 %, which suggests that this device is harvesting triplet excitons. This result indicates that carbazole dendrimers with attached acceptors are potential TADF materials owing to their polarized electronic structure (with HOMO–LUMO separation).     

A far-red emitting probe for unambiguous detection of mobile zinc in acidic vesicles and deep tissue

Imaging mobile zinc in acidic environments remains challenging because most small-molecule optical probes display pH-dependent fluorescence. Here we report a reaction-based sensor that detects mobile zinc unambiguously at low pH. The sensor responds reversibly and with a large dynamic range to exogenously applied Zn²⁺ in lysosomes of HeLa cells, endogenous Zn²⁺ in insulin granules of MIN6 cells, and zinc-rich mossy fiber boutons in hippocampal tissue from mice. This long-wavelength probe is compatible with the green-fluorescent protein, enabling multicolor imaging, and facilitates visualization of mossy fiber boutons at depths of >100 μm, as demonstrated by studies in live tissue employing two-photon microscopy.