Synthesis of new photoresponsive polyesters containing norbornadiene residues by the polyaddition of donor–acceptor norbornadiene dicarboxylic acid diglycidyl ester with dicarboxylic acids and their photochemical properties

A donor–acceptor norbornadiene derivative, 5‐(4‐methoxyphenyl)‐1,4,6,7,7‐pentamethyl‐2,5‐norbornadiene‐2,3‐dicarboxylic acid diglycidyl ester (D–A NDGE), was synthesized by the reaction of the cesium salt of 5‐(4‐methoxyphenyl)‐1,4,6,7,7‐pentamethyl‐2,5‐norbornadiene‐2,3‐dicarboxylic acid with epibromohydrin in N‐methyl‐ pyrrolidone (NMP). The polyaddition reactions of D–A NDGE with certain dicarboxylic acids were carried out with tetrabutylammonium bromide as a catalyst in NMP, producing corresponding polyesters containing D–A norbornadiene (NBD) residues in the main chain in fair to good yields. The photoisomerization of the D–A NBD residues in the polyesters proceeded very smoothly, forming the corresponding quadricyclane groups. The photoreactivities of the D–A NBD residues in the polymer were 50 times higher than those of the NBD residues in the film state and 60 times higher than those in a tetrahydrofuran solution. The stored energy in the quadricyclane groups of the polymers was about 45–55 kJ/mol according to differential scanning calorimetry analysis of the irradiated polymer films. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2683–2690, 2001     

Spectroscopic analyses and chemical transformation for structure elucidation of two novel indole alkaloids from Gelsemium elegans

Two new monoterpenoid oxindole alkaloids, gelsevanillidine (1) having an additional vanillin residue on gelsenicine-type alkaloid and gelseoxazolidinine (2) possessing an unusual oxazolidine ring, were isolated from Gelsemium elegans. To confirm their structures, the chemical transformation of a humantenine-type alkaloid into gelsevanillidine (1) and the deacetoxy derivative of gelseoxazolidinine was performed.     

Reversible micelle-vesicle conversion of oleyldimethylamine oxide by pH changes

A preliminary study on the reversible micelle-vesicle conversion of oleyldimethylamine oxide [Kawasaki, H. et al. J. Phys. Chem. B. 2002, 106, 1524 ] is extended in the present study. In the presence of 0.01 M NaCl at a surfactant concentration of 0.05 M, a micelle-to-vesicle conversion with increasing degree of ionization alpha takes place in the following sequence: growth of fibrous micelle (alpha < 0.2), a fused network (alpha approximately 0.3), fibrous micelles + (perforated) vesicles (alpha = 0.4), and vesicles + lamellae (alpha = 0.5). Viscoelasticity correspondingly varies from the Maxwell-type behavior of the entangled network of fibrous micelles to the gel-like behavior of vesicle suspensions, via a fluid solution-like behavior of the fused network. This phase sequence is in contrast with the case of no added salt where no branching of micelles is observed, and long micelles and bilayers (vesicles + lamellae) coexist at alpha = 0.5. In water, a state of the lowest viscoelasticity occurs around alpha = 0.2 for both surfactant concentrations 0.05 and 0.15 M. Synergism between protonated and nonprotonated amine oxide headgroups is observed despite low ionic strengths. From the time course of the reversible micelle-vesicle conversion, vesicles seem to be formed from threadlike micelles within 25 h according to the shear moduli, while a longer conversion time is suggested by a flow property (viscosity). Shear thickening behavior is observed at alpha = 0.2 and 0.4 in 0.01 M NaCl but not in water.     

Excited-states and lightfastness of linear trans-quinacridone pigment nanoparticles

The photoexcited state of linear trans-quinacridone pigment nanoparticles, prepared by a reprecipitation method, was analyzed by time-resolved spectroscopy. The analysis showed that the S₁ state of the linear trans-quinacridone nanoparticles undergoes a quantitative, non-radiative relaxation to the ground state with a time constant of about 100 ps. By contrast, the S₁ state of the molecular dispersion state (dilute solution state) was relatively long-lived (21 ns). This, together with the intersystem crossing to T₁ observed in the molecular dispersion state, clearly distinguished the nanoparticles from the molecular dispersion state. By comparing the two in terms of lightfastness, the nanoparticles were found to be much more lightfast than the molecular dispersion state. It was speculated that the superior lightfastness of the linear trans-quinacridone pigment nanoparticles was not due to the molecular structure but the facilitated S₁ relaxation by the aggregation of the molecules.     

Monodisperse and isolated microspheres of poly(N-methylaniline) prepared by dispersion polymerization

Monodisperse and isolated microspheres of poly(N-methylaniline) were successfully prepared through chemical polymerization of N-methylaniline by in adipic acid containing poly(vinylpyrrolidone) (PVP). Mean diameters of the microspheres with smooth surfaces changed from 320 to 100 nm by increasing the reaction temperature from 25 to 75 °C. The concentration of PVP did not affect much the size of microspheres, but the increased PVP concentration led to longer induction times for the onset of dispersion polymerization.     

Cobalt-catalyzed trimethylsilylmethylmagnesium-promoted radical alkenylation of alkyl halides: a complement to the Heck reaction

A cobalt complex, [CoCl2(dpph)] (DPPH = [1,6-bis(diphenylphosphino)hexane]), catalyzes an intermolecular styrylation reaction of alkyl halides in the presence of Me3SiCH2MgCl in ether to yield beta-alkylstyrenes. A variety of alkyl halides including alkyl chlorides can participate in the styrylation. A radical mechanism is strongly suggested for the styrylation reaction. The sequential isomerization/styrylation reactions of cyclopropylmethyl bromide and 6-bromo-1-hexene provide evidence of the radical mechanism. Crystallographic and spectroscopic investigations on cobalt complexes reveal that the reaction would begin with single electron transfer from an electron-rich (diphosphine)bis(trimethylsilylmethyl)cobalt(II) complex followed by reductive elimination to yield 1,2-bis(trimethylsilyl)ethane and a (diphosphine)cobalt(I) complex. The combination of [CoCl2(dppb)] (DPPB = [1,4-bis(diphenylphosphino)butane]) catalyst and Me3SiCH2MgCl induces intramolecular Heck-type cyclization reactions of 6-halo-1-hexenes via a radical process. On the other hand, the intramolecular cyclization of the prenyl ether of 2-iodophenol would proceed in a fashion similar to the conventional palladium-catalyzed transformation. The nonradical oxidative addition of carbon(sp2)-halogen bonds to cobalt is separately verified by a cobalt-catalyzed cross-coupling reaction of alkenyl halides with Me3SiCH2MgCl with retention of configuration of the starting vinyl halides. The cobalt-catalyzed intermolecular radical styrylation reaction of alkyl halides is applied to stereoselective variants. Styrylations of 1-alkoxy-2-bromocyclopentane derivatives provide trans-1-alkoxy-2-styrylcyclopentane skeletons, one of which is optically pure.     

Organocatalytic Activation of the Leaving Group in the Intramolecular Asymmetric SN2′ Reaction

A Brønsted‐acid‐catalyzed intramolecular enantioselective S_N2′ reaction was developed utilizing trichloroacetimidate as a leaving group. The findings indicated that dual activation of the substrates is operative. This metal‐free allylic alkylation allows highly enantioselective access to 2‐vinylpyrrolidines bearing various substituents.     

Crosstalk Reduction Using Tapered Intersecting Waveguides

Crosstalk reduction using tapered intersecting waveguides has been proposed and demonstrated experimentally. The crosstalk with a small intersection angle of up to 20° was theoretically investigated, by applying coupled mode theory. Experimental results show that the crosstalks between wide taper intersecting waveguides with the angles of 13 to 20° are decreased with respect to the crosstalk of the intersecting linear waveguide.