Nonclassical urea oligomers. I. Selective reactivity of 1-(N-substituted-carbamyl)aziridine for ring-transformation reactions and ring-opening polymerization

The reaction course of 1-(N-phenyl-carbamyl)aziridine with NaI was found to be highly sensitive to the nature of solvent used; e.g., acetone preferentially gives 1-phenyl-2-imidazolidinone, whereas dimethylformamide (DMF) gives 2-anilino-2-oxazoline. Nuclear magnetic resonance (NMR) study of the solvent effect revealed the relation between the site in the aziridine compound, with which the solvents interact, and the reaction products. From the results obtained by these ring-transformation studies, the use of diethyl sulfate, which is expected to solvate simultaneously at the carbonyl oxygen and the carbamyl–nitrogen atoms, resulted in polymerization of the monomer selectively to the oligomer of type—[CH₂CH₂N(CONHPh)]_n—. The diethyl sulfate was shown to play dual roles as a solvating reagent and an initiator. The oligomer obtained includes relatively definite amount (one molecule per ca. four monomer units) of diethyl sulfate in the “washed” state. The absorbed diethyl sulfate can be removed by treating with aqueous NaOH solution or Amberlite-400 column elution without altering the chemical constitution of the backbone in the polymer. Application of the polymerization procedure to several N-alkyl substituted monomers resulted in oligomers of a similar type. The difference in the monomer reactivity depending on the nature of the substituent groups can be due mainly to steric factors.     

Microhole-voltammograms Controlled by Solution Reservoir at Cationic and Anionic Ion Exchange Membranes

Microhole-voltammetry in which ions pass through a hole by electric migration exhibits rectified current-voltage curves. The rectification ratio, being of the high conductance to the low one, seems to depend on properties of ion exchange membranes. Our experiments at a cationic and an anionic membrane showed that the ratios for both the membranes were similar in spite of large difference in ionic capacities. The ratio was controlled by geometry of the reservoir of the solution rather than hole geometry and properties of membranes. Our model was composed of resistances of the hole, the membranes and the reservoir in series.     

Influence of Polarity and Rise Time of Pulse Voltage Waveforms on Diesel Particulate Matter Removal Using an Uneven Dielectric Barrier Discharge Reactor

The influence of polarity and rise time of the pulse voltage on the removal of particulate matter (PM) emitted from a diesel engine was investigated using a dielectric barrier discharge reactor. Four kinds of pulse voltage waveforms (positive, negative, positive–negative and negative–positive) were used. It was found that the energy efficiency for PM removal is just a function of energy injection and that there are no obvious influences on PM removal and energy efficiency within the voltage waveforms except the negative pulse voltage of a peak voltage below 8 kV. A comparison of PM removals using various kinds of pulse voltage waveforms and different types of plasma reactors is given.     

Stereospecific polymerization of benzyl vinyl ether by BF3·OEt2

Polymerization of benzyl vinyl ether was carried out by BF₃·OEt₂, and the effects of polymerization conditions on the stereoregularity of the polymer were studied by NMR analysis. The polymerization at ?78°C in toluene gave a highly isotactic polymer. The isotacticity of the polymer was independent of the catalyst concentration but increased with a decrease in the initial monomer concentration and decreased slightly on raising the reaction temperature. When the polymerizations were carried out in toluene—nitroethane mixtures, a gradual decrease in the isotacticity and a rapid decrease in the molecular weight of the polymer were observed with increasing nitroethane in the solvent. The molecular weight of the polymer was almost constant, regardless of the catalyst concentration, and increased with increasing initial monomer concentration and decreasing polymerization temperature. When the polymerization was performed in toluene at ?78°C with a small amount of water or benzyl alcohol, a linear relationship was found between the reciprocal DP of the polymer and water or benzylalcohol concentration. The mechanisms of the initiation reaction and the stereoregulation in the polymerization were also discussed.     

Preparation and properties of biocomposites composed of bio‐based epoxy resin,tannic acid,and microfibrillated cellulose

As new bio‐based epoxy resin systems, glycerol polyglycidyl ether (GPE) and sorbitol polyglycidyl ether (SPE) were cured with tannic acid (TA) at various conditions. When the curing conditions were optimized for the improvement of thermal and mechanical properties, the most balanced properties were obtained for the GPE/TA and SPE/TA cured at 160 °C for 2–3 h at the epoxy/hydroxyl ratio of 1/1. The cured SPE/TA had a higher glass transition temperature (T_g) and tensile strength than the cured GPE/TA. Next, biocomposites of GPE/TA and SPE/TA with microfibrillated cellulose (MFC) were prepared by mixing aqueous solution of the epoxy/curing reagent with MFC, and subsequent drying and curing at the optimized condition. For both the GPE/TA/MFC and SPE/TA/MFC biocomposites, T_g and the storage modulus at rubbery plateau region increased with increasing MFC content over the studied range of 3–15 wt %. The tensile strength at 25 °C for GPE/TA/MFC biocomposite with MFC content 10 wt % was 76% higher than that of control GPE/TA, while the tensile modulus was little improved. On the other hand, the tensile strength and modulus of SPE/TA/MFC biocomposite with MFC content 10 wt % were 30 and 55% higher than those of control SPE/TA, respectively. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 425–433, 2010     

Two new glycosides from the whole plants of Glechoma hederacea L

Two new glycosides, 7S,7'S,8R,8'R-icariol A(2)-9-O-beta-D-glucopyranoside (1) and 4-allyl-2-hydroxyphenyl 1-O-beta-D-apiosyl-(1-->6)-beta-D-glucopyranoside (2), were isolated from the dried whole plants of Glechoma hederacea L. (Labiatae) together with four known compounds, cistanoside E (3), dihydrodehydrodiconiferyl alcohol 4-O-beta-D-glucopyranoside (4), apigenin 7-O-beta-D-glucuronopyranoside (5) and luteolin 7-O-beta-D-glucopyranoside (6). The structures of the new compounds were elucidated on the basis of chemical and spectral analysis.     

Synthesis of immunoregulatory Helicobacter pylori lipopolysaccharide partial structures

The synthesis of immunoregulatory glycoconjugates, namely the active entity of lipopolysaccharide (LPS) from Helicobacter pylori was achieved. The results of biological activities of the LPS partial structures provide the structural basis for the immunobiological activity, especially for the immune inhibitory activity of H. pylori LPS.     

Algorithm for advanced canonical coding of planar chemical structures that considers stereochemical and symmetric information

We describe a rigorous and fast algorithm for advanced canonical coding of planar chemical structures based on the algorithm of Faulon et al. (J. Chem. Inf. Comput. Sci. 2004, 44, 427-436). Our algorithm works well even for highly symmetric structures; moreover, an advantage of our algorithm includes providing a rigorous canonical numbering of atoms with a consideration of stereochemistry and recognizing symmetric moieties. The planar structural line notation with the canonical numbering is also fit for use with stereochemical line notation. These capabilities are usable for general purposes in chemical structural coding and are particularly essential for detecting equivalent atoms in NMR studies. This algorithm was implemented on a 13C NMR chemical shift prediction system CAST/CNMR. Applications of the algorithm to several organic compounds demonstrate the practical efficiency of the rigorous coding.     

Computational SN2‐Type Mechanism for the Difluoromethylation of Lithium Enolate with Fluoroform through Bimetallic C−F Bond Dual Activation

The reaction mechanism for difluoromethylation of lithium enolates with fluoroform was analyzed computationally (DFT calculations with the artificial force induced reaction (AFIR) method and solvation model based on density (SMD) solvation model (THF)), showing an S_N2‐type carbon–carbon bond formation; the “bimetallic” lithium enolate and lithium trifluoromethyl carbenoid exert the C?F bond “dual” activation, in contrast to the monometallic butterfly‐shaped carbenoid in the Simmons–Smith reaction. Lithium enolates, generated by the reaction of 2 equiv. of lithium hexamethyldisilazide (rather than 1 or 3 equiv.) with the cheap difluoromethylating species fluoroform, are the most useful alkali metal intermediates for the synthesis of pharmaceutically important α‐difluoromethylated carbonyl products.     

Exhaustively methylated azacalix[4]arene: preparation, conformation, and crystal structure with exclusively CH/pi-controlled crystal architecture

[structure: see text]. Described are the preparation, conformation, and crystal structure of exhaustively methylated azacalix[4]arene involving nitrogen atoms as bridging units. NMR and X-ray crystallographic analysis have demonstrated that this novel azacalix[4]arene adopts a 1,3-alternate conformation both in solution and in the solid state. The crystal structure has been characterized solely by intermolecular CH/pi interactions, by which the azacalix[4]arenes mutually interact with each other outside the cavity to furnish a two-dimensional network structure.