Functional 1,3‐benzoxazine bearing 4‐pyridyl group: Synthesis and thermally induced polymerization behavior

1,3‐benzoxazine 1 , bearing 4‐pyridyl moiety on the nitrogen atom, was synthesized from p‐cresol, 4‐aminopyridine, and paraformaldehyde. The efficient synthesis was achieved by adding acetic acid to suppress the strong basicity caused by the presence of 4‐aminopyridine derivatives. Upon heating 1 at 180 °C, it underwent the thermally induced ring‐opening polymerization. The resulting polymer was composed of two types of repeating unit, i.e., (1) Mannich‐type one (‐phenol‐CH₂‐NR‐CH₂‐) that can be expected from the general ring‐opening polymerization of conventional benzoxazines and (2) a typical phenolic resin‐type one (‐phenol‐CH₂‐phenol‐) induced by release of 4‐aminopyridine and paraformaldehyde (unit B). Another structural feature of the polymer was that it possessed a benzoxazine moiety at the chain end. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 410–416     

Total Synthesis of the 7,10‐Epimer of the Proposed Structure of Amphidinolide N,Part II: Synthesis of C17–C29 Subunit and Completion of the Synthesis

The total synthesis of 7,10‐epimer of the proposed structure of amphidinolide N was accomplished. The requisite chiral C17–C29 subunit was assembled stereoselectively via Keck allylation, Shi epoxidation, diastereoselective 1,3‐reduction, and a later oxidative synthesis of the THF framework. The C1–C13 and C17–C29 subunits were successfully coupled using a Enders RAMP “linchpin” as the C14–C16 three carbon unit, thereby controlling the chirality at C14 and C16. The labile allyl epoxy moiety was successfully constructed by Grieco–Nishizawa olefination at a final stage of the synthesis.     

UV–vis and fluorescence detection by receptors based on an isophthalamide bearing a phenylethynyl group

We have successfully prepared 5-(2-phenylethynyl)isophathalilc acid as a signaling unit and the corresponding derivatives for an anion receptor 2 and a barbiturate receptor 4. Receptor 2 showed characteristic UV–vis changes and dramatic fluorescence quenching upon the addition of anions and receptor 4 showed UV–vis and an OFF-ON fluorescence changes upon the addition of dibutylbarbituric acid based on the diphenylethyne moiety.     

Polymeric Electron Carriers

Polymers containing 1,4-dihydronicotinamide (P-NAH) alloxan (P-A), and viologen (P-V²⁺) moieties were synthesized and characterized. P-NAH reduced various organic substances such as lipoic acid, alloxan, and viologens and also immobilized quinone mediated by alloxan. P-A was reduced to the polymer-bearing alloxan radical and the dialuric acid structure without crosslinks by one- and two-electron reduction, respectively, and P-A also mediated the redox reaction occurring between aqueous and organic (water-immiscible) layers. P-V²⁺ was converted to the stable viologen radical reversibly by one-electron reduction. Electric potentials and currents on photo-reduction of P-V²⁺ and catalytic behavior of P-V²⁺ in the reduction of carbonyl compounds were examined.     

Determination of oil–water partition coefficients of polar compounds: silicone membrane equilibrator vs. SPME passive sampler

Experimental determination of oil-water partition coefficients often poses difficulties associated with emulsion formation. The aim of this work was to find an appropriate technique for determination of oil–water partition coefficients of polar, nonvolatile compounds. Two different methods were tested. The first method used a “silicone membrane equilibrator.” For the second method, solid-phase microextraction (SPME) fibers with a polyacrylate (PA) coating were used as a passive sampler. With both methods, oil–water partition coefficients for 14 compounds with polar functional groups were determined at 37 °C with good repeatability (standard deviation 0.11 log units or lower). The partition coefficients determined with the silicone membrane equilibrator method ranged from 0.50 to 3.49 log units. The oil–water partition coefficients obtained with the PA-SPME passive sampling approach were significantly higher than those obtained with the silicone membrane equilibrator method for nine of 14 compounds. The differences were up to 0.39 log units (i.e., a factor of 2.5). Additional experiments suggested that this difference occurred because the sorption properties of the PA fibers used were influenced by the surrounding phase, e.g., through swelling of the polymer phase. Therefore, the SPME passive sampling method using PA fibers seems to be less reliable, whereas the silicone membrane equilibrator method was found to be a convenient technique for the determination of oil–water partitioning.     

Structural Fluctuation of Disilanyl Double‐Pillared Bisheteroarenes

Silacyclophanes possessing two disilanyl pillars were synthesized from tricyclic heteroarenes in one‐pot synthetic procedures. The step‐like anti structures of three congeners bearing two heteroarene units were revealed in single crystals by X‐ray crystallographic analysis. Depending on the structures of aromatic units, torsion angles at the disilanyl pillars altered to maintain the overall step‐like molecular structures. The structure, however, fluctuated between anti and syn conformers in a solution phase despite the presence of eight methyl groups on the ring periphery. The analysis of the coalescence temperature with NMR spectroscopy showed the fundamental energetics of the dynamics. The subtle structural differences affected the dynamic behavior of the silacyclophanes.