X-ray and IR studies on crystal and molecular structure of 4-nitro-2,6-diphenylphenol. Stereochemistry of bifurcated OH⋯π hydrogen bonds

The crystals of the title compound contain both intra- and inter-molecular OH?π hydrogen bonds (the first example of bifurcated OH?π bonds), the stereochemistry of which has been elucidated by an X-ray structure analysis; this bifurcated bond is also supported by the observation based on the IR spectrum of the crystals.     

Synthetic studies on β-lactam antibiotics. VII. Mild removal of the benzyl ester protecting group with aluminum trichloride

The benzyl ester protecting group in β-lactam derivatives can be cleanly removed by treatment with aluminum trichloride under mild conditions, preferably in the presence of anisole, to give the corresponding free acids in high yields.     

Preparation of chiral 5-deazaflavin derivatives and their asymmetric reduction of ethyl benzoylformate

1,5-Dihydro-5-deazaflavin derivatives possessing a chiral substituent at N(3) position were synthesized, with which moderate asymmetric induction was observed in the reduction of ethyl benzoylformate.     

The rise process of the electric birefringence of poly-γ-benzyl-l-glutamate at high fields

Summary The rise process, steady-state and decay process of the birefringence of poly--benzyl-l-glutamate solutions under the action of a rectangular pulse have been studied at 25 °C over a wide range of field strength of 1.5×10³ to 3×10⁴V/cm. The solvent used was a dichloroethane-dimethylformamide mixture of the volume ratio 991. From the decay process the average relaxation time extrapolated to zero concentration and the corresponding rotational diffusion constant were determined. The apparent dipole moment and the optical anisotropy factor were obtained from the field strength dependence of steady-state birefringence. The rise process was analyzed according to our theory which holds for arbitrary high field strength in the initial stage. The n(t)/t versus t curves for various field strengths were found to be linear in the initial stage and pass through the origin. Thus, it was concluded that the electrical orientation of poly--benzyl-l-glutamate in solution is due primarily to the permanent dipole moment. Furthermore, the value of the apparent permanent dipole moment obtained from the rise process was compared with that obtained from the steadystate birefringence.

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Zusammenfassung Der Einschaltvorgang, der stationäre Zustand und das Abklingen der Doppelbrechung bei Poly--benzyl-l-glutamat-Lösungen mit einem elektrischen Impuls von rechteckiger Form werden bei 25 °C über einem großen Feldstärkebereich von 1.5×10³–3×10⁴V/cm untersucht. Als Lösungsmittel wird die Dichloräthan/Dimethylformamid-Mischung im Volumenverhältnis 991 verwendet. Aus dem Abklingvorgang werden die zur Konzentration 0 extrapolierte mittlere Relaxationszeit und die entsprechende Rotationsdiffusionskonstante bestimmt. Das scheinbare permanente Dipolmoment und der optische Anisotropiefaktor werden aus der Feldstärkeabhängigkeit der stationären Doppelbrechung ermittelt. Der Einschaltvorgang wird nach unserer Theorie, die für beliebige hohe Feldstärken im Anfangsverlauf gültig ist, analysiert. Die n(t)/t gegen t-Kurven für verschiedene Feldstärken sind geradlinig im Anfangsverlauf und laufen durch den Ursprung. Hieraus zeigt sich, daß die elektrische Orientierung von Poly--benzyl-l-glutamat in Lösungen hauptsächlich durch das permanente Dipolmoment bedingt ist. Überdies wird der aus dem Einschaltvorgang gewonnene Wert des scheinbaren permanenten Dipolmomentes mit dem aus der stationären Doppelbrechung ermittelten Wert verglichen.

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With 7 figures     

Synthesis of 1-beta-O-acyl glucuronides of diclofenac, mefenamic acid and (S)-naproxen by the chemo-selective enzymatic removal of protecting groups from the corresponding methyl acetyl derivatives

Using a straightforward chemo-enzymatic procedure, 1-beta-O-acyl glucuronides of three non-steroidal anti-inflammatory drugs, diclofenac (DF) 5, mefenamic acid (MF) 6 and (S)-naproxen (NP) 7, were prepared. Caesium salts of these carboxylic acid drugs reacted with commercially available methyl 2,3,4-tri-O-acetyl-1-bromo-1-deoxy-alpha-D-glucopyranuronate 4 to give exclusively the corresponding 1-beta-O-acyl glucuronides 8-10 in moderate yields. The protecting acetyl (for -OH group) and methyl ester (for -CO2H group) groups of each sugar moiety were easily removed to provide the corresponding free 1-beta-O-acyl glucuronides 1-3 in high yields. Deprotection was achieved through effective enzyme-catalysed chemo-selective hydrolyses of the acetyl groups using lipase AS Amano (LAS), and of the methyl ester group using esterase from porcine liver (PLE).     

Beta-1,3-glucan polysaccharide (schizophyllan) acting as a one-dimensional host for creating supramolecular dye assemblies

We have demonstrated that one-dimensional supramolecular dye assemblies with a uniform diameter can be created by utilizing schizophyllan (SPG) as a one-dimensional host. In the supramolecular nanofibers, the dye molecules are assembled into the different aggregation modes depending on the preparation procedures. The findings establish that SPG is useful for creating the supramolecular nanofibers, where temporal superstructures can be stabilized by the SPG-specific helical higher-order structure. [structure: see text].