Synthesis and central nervous system stimulant activity of 5,8-methanoquinazolines fused with imidazole,thiadiazole, pyrimidine and 1,3,5-triazine

5,8-Methanoquinazolines fused with imidazoles 4a-4b , thiadiazoles 5–6 , pyrimidines 7, 9, 11 and 12 , and 1,3,5-triazine 13 were prepared starting from (5R,8S)-2-amino-8,9,9-trimethyl-5,6,7,8-tetrahydro-5,8-methanoquinazoline 3 . Most compounds possessed central nervous system stimulant activities.     

Synthesis of fluorine‐containing star‐shaped poly(vinyl ether)s via arm‐linking reactions in living cationic polymerization

Various types of fluorine‐containing star‐shaped poly(vinyl ether)s were successfully synthesized by crosslinking reactions of living polymers based on living cationic polymerization. Star polymers with fluorinated arm chains were prepared by the reaction between a divinyl ether and living poly(vinyl ether)s with fluorine groups (C₄F₉, C₆F₁₃, and C₈F₁₇) at the side chain using cationogen/Et_1.5AlCl_1.5 in a fluorinated solvent (dichloropentafluoropropanes), giving star‐shaped fluorinated polymers in high yields with a relatively narrow molecular weight distribution. The concentration of living polymers for the crosslinking reaction and the molar feed ratio of a bifunctional vinyl ether to living polymers affected the yield and molecular weight of the star polymers. Star polymers with block arms were prepared by a linking reaction of living block copolymers of a fluorinated segment and a nonfluorinated segment. Heteroarm star‐shaped polymers containing two‐ or three‐arm species were synthesized using a mixture of different living polymer species for the reaction with a bifunctional vinyl ether. The obtained polymers underwent temperature‐induced solubility transitions in various organic solvents, and their concentrated solutions underwent sol–gel transitions, based on the solubility transition of a thermoresponsive fluorinated segment. Furthermore, a slight amount of fluorine groups were shown to be effective for physical gelation when those were located at the arm ends of a star polymer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Ethylbenzene solubility,diffusivity, and permeability in poly(dimethylsiloxane)

The pure‐gas sorption, diffusion, and permeation properties of ethylbenzene in poly(dimethylsiloxane) (PDMS) are reported at 35, 45, and 55 °C and at pressures ranging from 0 to 4.4 cmHg. Additionally, mixed‐gas ethylbenzene/N₂ permeability properties at 35 °C, a total feed pressure of 10 atm, and a permeate pressure of 1 atm are reported. Ethylbenzene solubility increases with increasing penetrant relative pressure and can be described by the Flory–Rehner model with an interaction parameter of 0.24 ± 0.02. At a fixed relative pressure, ethylbenzene solubility decreases with increasing temperature, and the enthalpy of sorption is −41.4 ± 0.3 kJ/mol, which is independent of ethylbenzene concentration and essentially equal to the enthalpy of condensation of pure ethylbenzene. Ethylbenzene diffusion coefficients decrease with increasing concentration at 35 °C. The activation energy of ethylbenzene diffusion in PDMS at infinite dilution is 49 ± 6 kJ/mol. The ethylbenzene activation energies of permeation decrease from near 0 to −34 ± 7 kJ/mol as concentration increases, whereas the activation energy of permeation for pure N₂ is 8 ± 2 kJ/mol. At 35 °C, ethylbenzene and N₂ permeability coefficients determined from pure‐gas permeation experiments are similar to those obtained from mixed‐gas permeation experiments, and ethylbenzene/N₂ selectivity values as high as 800 were observed. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1461–1473, 2000     

Living cationic ring-opening polymerization by water-stable initiator: synthesis of a well-defined optically active polythiourethane

Living cationic ring-opening polymerization under air and water was achieved using a well-defined water-resistant cationic initiator in dichloromethane without purification at ambient temperature.     

Enantioselective total synthesis of (−)-pseudophrynaminol through tandem olefination, isomerization and asymmetric Claisen rearrangement

A new and efficient total synthesis of (−)-pseudophrynaminol, the pyrrolo[2,3-b]indole alkaloid bearing the allylic moiety at the 3a-position, has been achieved by a sequence involving 3-allylindol-2-one 8 as a key intermediate. The enantioselective construction of the quaternary carbon in 8 was performed through a tandem cascade reaction of 2-allyloxyindolin-3-one 4, olefination, isomerization, and asymmetric Claisen rearrangement.     

Gas permeation of fullerene‐dispersed poly(1‐trimethylsilyl‐1‐propyne) membranes

Homogeneously fullerene‐dispersed membranes were prepared under the conditions in which a 10 wt % poly(1‐trimethylsilyl‐1‐propyne) solution containing 0.5 wt % fullerene was dried under a reduced pressure of 50 cmHg at 100 °C. UV‐vis spectra and microscopic observations of the fullerene membranes indicated that the fullerene was homogeneously dispersed in the membranes. The permeability coefficients of 1‐butene were found to be higher than those of n‐butane in the fullerene membranes, although the permeability coefficients of olefin gases were nearly equal to those of paraffin gases having the same number of carbon in poly(1‐trimethylsilyl‐1‐propyne) membranes containing no fullerene. Pressure dependence of permeability coefficients was clearly observed for the permeation of carbon dioxide, ethylene, ethane, 1‐butene, and n‐butane through the fullerene membranes, while no significant dependence was found for poly(1‐trimethylsilyl‐1‐propyne) membranes except for the permeation of 1‐butene and n‐butane. The pressure dependence of the permeability was explained by the dual‐mode sorption model. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1749–1755, 2000     

Chromium- and tungsten-triggered valence isomerism of cis-1-acyl-2-ethynylcyclopropanes via [3,3]sigmatropy of (2-acylcyclopropyl)vinylidene-metal intermediates.

The reaction of cis vicinal acetylethynylcyclopropanes 1 with a catalytic amount of M(CO)5(THF) (M = Cr or W) in the presence of Et3N at room temperature gave ortho-substituted phenols 7 in good yields as valence isomerized products. In the absence of Et3N the reactions did not work at all. The reaction of a cyclopropane having an ester or an amide instead of an acetyl moiety with M(CO)5(THF) did not take place, whereas an ethynylvinylcyclopropane gave a mixture of 1- and 2-substituted 1,3,5-cycloheptatrienes. These valence isomerization reactions are assumed to proceed via the formation of vinylidene-metal intermediates 2 from terminal alkynyl moieties followed by [3,3]sigmatropy of 2 to give seven-membered carbene complexes 3.     

New mu-opioid receptor agonists with phenoxyacetic acid moiety

New muq-opioid receptor (MOR) agonists containing 4-hydroxypiperidine, piperidine and piperazine moieties were synthesized and evaluated to find a peripheral opioid analgesic. Among the synthesized compounds, 12-[1-[3-(N,N-dimethylcarbamoyl)-3,3-diphenylpropyl]-4-hydroxypiperidin-4-yl]phenoxy]acetic acid (8: SS620) having phenoxyacetic acid and 4-hydroxypiperidine moieties showed the highest agonist potency on the MOR in an isolated guinea-pig ileum preparation, and it also had selectivity to the human MOR expressed in Chinese hamster ovary (CHO)-K1 cells compared with the same types of delta- and kappa-opioid receptors (DOR and KOR). In addition, compound 8 showed a 10 times more potent MOR agonist activity than loperamide. Furthermore, compound 8 showed a peripheral analgesic activity in vivo screening on rat.     

Purification of Food Color Red No. 106 (acid red) using pH-zone-refining counter-current chromatography

pH-Zone-refining counter-current chromatography was successfully applied to the separation of the main components of Food Color Red No. 106 (R-106, acid red, Color Index No. 45100). A 300-mg quantity of sample was separated using the following two-phase solvent system: n-butanol-water, 40 mM sulfuric acid in organic stationary phase and 30 mM ammonia in aqueous mobile phase. The obtained fractions were analyzed by high-performance liquid chromatography and fast atom bombardment mass spectrometry. The separation yielded 261.9 mg of main component of acid red with purity of 99.9%.