Aqueous hydroxide as a base for palladium-catalyzed amination of aryl chlorides and bromides

The amination of aryl halides in the presence of inexpensive and air-stable alkali metal hydroxide bases and Pd[P(t-Bu)3]2 as catalyst gave arylamines in high yields. The reactions were conducted with a catalytic amount of cetyltrimethylammonium bromide as phase-transfer agent and either aqueous hydroxide or solid hydroxide in the presence of water. This combination of alkali metal hydroxide base, H2O, and the ammonium salt performed as well as NaO-t-Bu in the amination of p-chlorotoluene with dibutylamine. Hydroxide base was suitable for reactions of a wide range of aryl chlorides and bromides with aliphatic and aromatic amines. Some functional groups that were intolerant of tert-butoxide base, such as esters, enolizable ketones, nitriles, and nitro groups, were tolerated by the combination of hydroxide base, H2O, and cetyltrimethylammonium bromide in toluene solvent.     

Synthesis of 2,2'-dihydroxybisphenols and antiviral activity of some bisphenol derivatives

New diphenylmethane-type 2,2'-dihydroxybisphenols (5a-d) were prepared regioselectively in good yields. We evaluated the antiviral activity of some bisphenol derivatives synthesized by the plaque reduction assay. Most of the compounds showed significant antiviral activity and the 4,4'-dihydroxybisphenol derivative (10) showed higher activity than 2,2'-bisphenol derivatives. This compound had EC50 value of 1.8 microg/ml.     

Photoluminescence switching of azobenzene-conjugated Pt(II) terpyridine complexes by trans-cis photoisomerization

Pt(II) complexes with a terpyridylazobenzene ligand (tpyAB) were newly synthesized, and their photoluminescence properties by trans-cis isomerization of the azo moiety were investigated. In these complexes, upon excitation with 366-nm light in polar solvents such as DMF, DMSO, and propylene carbonate, trans-to-cis isomerization with significant UV-vis spectral changes occurred almost completely. Cis-to-trans isomerization was observed both by irradiation with visible light and by heat. The reduction peaks due to the terpyridine and the azo group in the cyclic voltammograms of the Pt complexes were shifted in the positive direction by trans-to-cis isomerization. Emission spectral changes due to trans-cis isomerization were observed for both the tpyAB and the Pt complexes. The significant differences in the emission properties of the complex compared to tpyAB include the observation that both the excitation and emission wavelengths were shifted to lower energy, located in the visible region. Moreover, the change in emission intensity between the trans and cis forms was more significant upon excitation with UV light, because the trans form of the complexes showed absolutely no emission. Accordingly, the azobenzene-conjugated Pt(II) terpyridine complexes promise to be doubly photofunctional materials, showing complete off-on switching of emission linked to the trans-cis conformation change.     

Reversible activity changes of lipid-coated lipase for enantioselective esterification in supercritical fluoroform

Enzymatic activity of a lipid-coated lipase for enantioselective esterification of (R)-1-phenylethanol in supercritical fluoroform can be reversibly controlled by changing pressure or temperature that reflects changes of dielectric constant.     

First and second generation total synthesis of the teicoplanin aglycon.

Full details of studies leading to the total synthesis of the teicoplanin aglycon are provided. Key elements of the first generation approach (26 steps from constituent amino acids, 1% overall) include the coupling of an EFG tripeptide precursor to the common vancomycin/teicoplanin ABCD ring system and sequential DE macrocyclization of the 16-membered ring with formation of the diaryl ether via a phenoxide nucleophilic aromatic substitution of an o-fluoronitroaromatic (80%, 3:1 atropisomer diastereoselection) followed by 14-membered FG ring closure by macrolactamization (66%). Subsequent studies have provided a second generation total synthesis which is shorter, more convergent, and highly diastereoselective (22 steps, 2% overall). This was accomplished by altering the order of ring closures such that FG macrolactamization (95%) preceded coupling of the EFG tripeptide to the ABCD ring system and subsequent DE ring closure. Notably, DE macrocyclization via diaryl ether formation on substrate 57, the key intermediate in the latter approach incorporating the intact FG ring system, occurred with exceptional diastereoselection for formation of the natural atropisomer (>10:1, 76%) without problematic C(2)(3) epimerization provided the basicity of the reaction is minimized.     

Synthesis and hydrolysis of p‐toluoyl and acetyl 9‐triptycyl diselenides: A study on generation of triptycene‐9‐selenenoselenoic acid

p‐Toluoyl 9‐triptycyl diselenide ( 9 ) was prepared by reaction of Se‐9‐triptycyl triptycene‐9‐selenoseleninate ( 7 ) with p‐toluenecarboselenoic acid ( 8 ) and by reaction of triptycene‐9‐selenenoselenolate salt with p‐toluoyl chloride. Acetyl 9‐triptycyl diselenide ( 13 ) was prepared by reaction of triptycene‐9‐selenenoselenolate salt with acetyl chloride. Hydrolysis of the two diselenides, 9 and 13 , provided triptycene‐9‐selenol ( 10 ) and di‐9‐triptycyl triselenide ( 12 ), suggesting the generation of triptycene‐9‐selenenoselenoic acid ( 3 ). © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:525–528, 2005; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20155     

Infrared-laser delivery system based on polymer-coated hollow fibers

Infrared Er : YAG laser delivery systems based on hollow fibers with an internal polymer layer has been developed. The system consists of a hollow fiber as the delivery medium, a launching coupler for effective coupling between the laser beam and the fiber, and a sealed hollow-fiber tip attached at the output end of the fiber. Fabrication process of the fiber and attachment of the delivery system is reported.     

Instabilities Driven by an Intense Beam in a Plasma-Filled Dielectric-Lined Waveguide Immersed in a Finite Axial Magnetic Field

A linear analysis is described on stabilities driven by an intense relativistic electron beam in an infinitely long, plasma-filled, and dielectric-lined circular waveguide immersed in a finite strength axial magnetic field. A dispersion equation is derived from the cold fluid theory and solved numerically. Beam-plasma instabilities due to interaction between beam modes and the Trivelpiece-Gould modes appear as well as the Cherenkov and the cyclotron Cherenkov instabilities. Parametric researches are carried out varying magnetic field strength, plasma density, and dielectric constant. Effects of a finite magnetic field and plasma filling are discussed in connection with the possibilities of using this system as a microwave radiation source.     

Titanium Dioxide Nanoparticles Produced in Water-in-oil Emulsion

Titanium dioxide (titania) particles were prepared by a water-in-oil emulsion system, and studied for the photodecomposition property of methylene blue. Microemulsion (ME) consisted of water, cyclohexane or octane, and surfactant, such as polyoxyethylene (10) octylphenyl ether (TX-100), polyoxyethylene lauryl ether, or bis (2-ethylhexyl) sodium sulfosuccinate. Titanium tetraisopropoxide (TTIP) was dropped into the ME solution and then titania particles were formed by the hydrolysis reaction between TTIP in the organic solvent and the water in the core of ME. It was found that ME could be classified to the reversed micelle (RM) region and the swelling reversed micelle (SM) region according to the water content. The water droplets in RM were almost monodispersed, where the water content was small. On the other hand, the water droplets in SM had a size distribution, although most of the water molecules associated with surfactant molecules. The size of the particles prepared in the RM region was smaller than the ME size. In contrast, the size of the particles formed in the SM region was larger than the ME size, and coagulation of the particles was observed within a few hours. The smallest diameter of the particles was 2 nm in the system of cyclohexane with TX-100 surfactant when the molar ratio of water to surfactant was 2. Titania particles prepared in this condition were collected as amorphous powder, and converted to anatase phase at less than 500 K, which is lower than the ordinal phase transition temperature. These anatase phase titania particles only showed a significant photodecomposition of methylene blue by illumination with a Xenon lamp.