Substituent effects on the tautomer ratios between the enamine and methylene imine forms in side-chained quinoxalines

The p- and m-substituted 3-arylcarbamoylmethylene-2-oxo-1,2,3,4-tetrahydroquinoxalines 3a-o showed the tautomeric equilibria between the enamine C and methylene imine D forms in dimethyl sulfoxide or dimethyl sulfoxide/trifluoroacetic acid media. The linear correlation of the Hammett σ_p and σ_m values with the log K_T values was observed in the dimethyl sulfoxide/trifluoroacetic acid (2:1) media of compounds 3a-o , wherein K_T meaned the tautomeric equilibrium constants ([D]/[C]).     

Selective hydrogenation of carbon monoxide to light olefins catalyzed by supported potassium tetracarbonylhydridoferrate

In the Fischer-Tropsch synthesis, potassium tetracarbonylhydridoferrate, KHFe (CO)₄, supported on HY-zeolite or silica gel exhibited high selectivity to light olefins without following the Schulz-Flory distribution.

---

, KHFe(CO)₄, HY —, — .

     

Temperature and solvent control of the stereoselectivity in the reactions of singlet oxygen with oxazolidinone-substituted enecarbamates

Oxazolidinone-functionalized enecarbamates react stereoselectively with singlet oxygen to give methyldesoxybenzoin (MDB) in moderate to high enantiomeric excess. The stereochemical outcome depends on the E/Z substrate geometry, temperature, and solvent variables. The analysis of the differential activation parameters suggests a large contribution from the entropy term in determining the enantioselectivity. We demonstrate the utility of the temperature and solvent variables in determining the degree of the photochemical kinetic resolution of the enecarbamates; for example, in the photooxygenation at -70 degrees C in methanol, MDB may be obtained in methanol.     

Hydrolysis and condensation reactions of Si(OC2H5)4 related to silica fiber drawing

The hydrolysis and condensation reactions of Si(OC₂H₅)₄ (TEOS) at 80°C in the TEOS---H₂O---C₂H₅OH---HCl solutions with H₂O/TEOS molar ratios (r) from 1.0 to 2.0 were followed by gas chromatography (GC) and measurement of molecular weight ( ) of the hydrolyzates, in order to explain the viscosity change of the solutions. It has been found that the siloxane oligomers with average polymerization degree (n) from 2 to 7 are formed in the early stage of reaction and undergo condensation to form higher polymers. The n and the number of silanol groups of the oligomers are increased with increasing r. The fact that the solution viscosity increased once rapidly around the so-called gelation point followed by a sluggish increase with the increase of reaction time for an r of 1.7, while it increased rapidly without a break till gelation for an r of 2.0, was attributed to fewer silanol groups and higher steric hindrance as a result of more −OC₂H₅ groups remaining in the oligomers for an r of 1.7.     

Novel emulsion graft copolymerization onto the silylmethyl group of poly(dimethylsiloxane)

The influence of radical initiators upon the emulsion graft copolymerization of styrene and acrylonitrile onto poly(dimethylsiloxane) (PDMS) was studied. As initiators, a series of peroxides and hydroperoxides were coupled with ferrous sulfate, among which the tert-butyl peroxylaurate system gave the highest grafting efficiency (30%). The tert-butyl peroxylaurate initiator fulfills the criteria for efficient radical grafting by generating only the tert-butoxy radical, which is reluctant to form a carbon radical via β-scission, being highly hydrophobic, and not carrying a tertiary hydrogen that may be abstracted by a radical. ¹³C-NMR analysis of the products showed that the grafting occurred on the silylmethyl groups of PDMS to give 10–25 grafts per polymer and graft ratio in the range 44–140%. The PDMS graft copolymers thus obtained could be used as surface-modifying agents to improve the lubricity and water-repellency of ABS [poly(styrene-co-acrylonitrile)-graft-polybutadiene]. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2607–2617, 1997     

Ring transformation of 3-halo-4-methoxycoumarins into pyrazoles with hydrazines

3-Chloro- and 3-bromo-4-methoxycoumarins 1a,b were readily transformed into 4-halo-5-(2-hydroxyphenyl)-3-oxo-2,3-dihydropyrazoles 2a,b with hydrazines. In the reaction of 1a,b with excess hydrazine and phenylhydrazine in boiling ethanol, unexpected 4-hydrazono-3-(2-hydroxyphenyl)-2-pyrazolin-5-ones 3 , 5 were obtained. The structure of 3 was determined by X-ray diffraction analysis.     

Concept of Photorefractive Connection Module by Photorefractive Four-Wave Mixing with Extraordinary Writing Beams and an Ordinary Reading Beam

We propose a new optical network device photorefractive connection module (PRCM) which operates as optical switch, amplifier and signal distributor controlled by parallel optical signals. Simple optical control bus systems can be realized by cascade connection of PRCMs. PRCM branches off a desired channel from the spatial multiplexed optical bus line by appropriate setting of the control beam pattern. PRCM uses cross polarized four wave mixing (CPFWM) with extraordinary polarized writing beams and an ordinary polarized reading beam to achieve a high connection gain to the next PRCM stage. We analyze the phase matching angle of CPFWM in which the optical paths of two pump beams are slightly different. The phase conjugate reflectivity indicating a branching ratio of optical signal is derived and calculated in consideration of the phase mismatching Δk. The optimum pump ratio and the grating vector orientation for the largest phase conjugate reflectivity and signal amplification factor are discussed for optical design of PRCM. Since the measured signal beam power after passing through the BaTiO₃ crystal is three or four times higher than its incident power, PRCM has a sufficient connection gain for optical bus and interconnection systems.     

A new triterpene and a saponin from Centella asiatica

A new triterpene and a saponin,named 2α,3β,23-trihydroxyurs-20-en-28-oic acid(1)and 2α,3β,23-trihydroxyurs-20-en-28-oic acid O-α-L-rhamnopyranosyl-(1→4)-O-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl ester(2),have been isolated from the aerial part of Centella asiatica.Their structures were elucidated by spectral methods,including 2D-NMR spectra.