Oxythallation of norbornene derivatives with thallium(III) acetate in methanol

Treatment of norbornene, norbornadiene, benzonorbornadiene, and chloro- and methoxy-benzonorbornadiene with thallium(III) acetate in methanol affords only the corresponding cis-exo-acetoxythallation adducts in a sharp contrast to oxymercuration of such strained olefins where methoxymercuration prevails. In the cases of substituted benzonorbornadienes the products are obtained as the regioisomeric mixtures, the isomer ratio being determined by ¹³C NMR. In the cases of 5-norbornene-2,3-dicarboxylic anhydride, 5-norbornene-2-methyl-2,3-dicarboxylic anhydride, and 5-norbornen-2-endo-carboxylic acid, lactonization occurs to give a trans-oxythallation adduct having a lactone ring, no introduction of either methoxy or acetoxy groups being observed. ¹H and/or ¹³C NMR data for several new oxythallation adducts are provided. The alkaline sodium borohydride reduction of adducts in methanol affords mainly the parent olefin together with 10–16% yields of the corresponding exo-alcohol.     

Thermoswitching property in TCNQ salts of ionenes containing poly(ethylene oxide) segments

Ionene polymers characterized by the alternating structure of ionene and crystalline poly(ethylene oxide) (PEO) segments were prepared as a function of PEO segment size. A microstructure of these ionenes and their 7,7,8,8-tetracyanoquinodimethane (TCNQ) salts were investigated with x-ray diffraction patterns, thermal scanning behavior, and polarizing micrographs. On the basis of this microstructure, the change in resistivity with temperature was studied. In Arrhenius' plots of the resistivity the simple salts in which the spherulites consisting of the PEO segments were observed showed a sharp decrease in resistivity with a rise in temperature [critical temperature resistor (CTR)] at about the melting point of the PEO segments, whereas the other simple salts in which the spherulites were not observed showed linear temperature dependence. The switching properties were confirmed similarly in repetitive heating/cooling cycles. This CTR characteristic was attributed to an increase in continuity in the conduction paths by melting spherulites. The apparent switching properties were not observed in the complex salts.     

Incorporation of CdS Nanoparticles Formed in Reverse Micelles into Mesoporous Silica

The incorporation of CdS nanoparticles, prepared in reverse micellar systems, into thiol-modified mesoporous silica, such as FM41 (functionalized MCM-41) and FM48 (functionalized MCM-48), has been investigated. The nanoparticles were immobilized in the mesopores via the incorporation of water droplets of the reverse micelles. A particle-sieving effect for FM41 having large (L-FM41, 3.8 nm) and medium (M-FM41, 3.6 nm) pore size was observed, in that the incorporation of the CdS nanoparticles was decreased with increasing particle size and with decreasing pore size of the FM41. Chemical vapor deposition treatment employed to narrow the mesopores of the CdS-FM41 enhanced the stability of CdS nanoparticles against heat treatment. The CdS-FM41 composites demonstrated photocatalytic activity for H(2) generation from 2-propanol aqueous solution, the better photocatalytic activity being obtained with the larger pore size for CdS-L-FM41. Copyright 2001 Academic Press.     

Computer simulation for the cooligomerization system

In order to clarify the kinetic features of the styrene (A)–methyl methacrylate (B)–CCl₄(S) cooligomerization system, a computer simulation was carried out. The experimental data on the degree of polymerization and the deviation of the cooligomer composition from the statistical steady-state composition were comparatively well explained by calculations based on the kinetic equations derived from the assumed reaction scheme and the values of the velocity coefficients, although the values of the four velocity coefficients in the initiation step and the velocity coefficient of the termination by the coupling of two solvent radicals were estimated. The results of the calculation of the rate of each component reaction show that the following two reactions are the most important in the initiation and in the transfer and termination steps when the [S]/([A] + [B]) ratio is large: where, A, A*, and P are styrene, polystyryl radical, and the cooligomer, respectively. Moreover, it was concluded that the deviation of the cooligomer composition from the statistical steady-state composition was caused by these two reactions.     

On the use of methyl substituted poly(vinylnaphthalene) as a reversible singlet oxygen carrier

Poly(1,4-dimethyl-6-vinylnaphthalene) and poly(1,2,4-trimethyl-6-vinylnaphthalene) react with singlet oxygen to give corresponding endoperoxide polymers which on warming generate singlet oxygen efficiently. Singlet oxygenations by the use of these polymers have been described.     

Interaction of Enzyme with Polymer Matrix in Immobilized Enzymes

Thermolysin was immobilized by radiation polymerization of hydroxyalkyl acrylate and tetradecaethylene glycol dimethacrylate monomers at low temperatures in the presence of the enzyme, and the degree of interaction of the enzyme with the polymer matrix was studied by measuring the thermal stability of the immobilized enzyme. The thermal stability was affected by the molecular structure of the monomer; the thermal stability of the immobilized enzyme from hydrophilic monofunctional monomers in the wet state was higher than that from hydrophobic bifunctional monomers. The thermal stability in polymers formed from hydroxy-alkyl acrylates decreased with an increase in the number of methylene units in the monomer, owing to a change of the state of the enzyme trapped in the porous polymer matrix. The enzyme molecule trapped in a hydrophilic porous polymer matrix appeared to be stabilized by interaction with the polymer chains.     

Adsorption and reactions of NO on clean and CO-precovered Ir(111)

Adsorption and reactions of NO on clean and CO-precovered Ir(111) were investigated by means of X-ray photoelectron spectroscopy (XPS), high-resolution electron energy loss spectroscopy (HR-EELS), infrared reflection absorption spectroscopy (IRAS), and temperature-programmed desorption (TPD). Two NO adsorption states, indicative of fcc-hollow sites and atop sites, were present on the Ir(111) surface at saturation coverage. NO adsorbed on hollow sites dissociated to Na and Oa at temperatures above 283 K. The dissociated Na desorbed to form N2 by recombination of Na at 574 K and by a disproportionation reaction between atop-NO and Na at 471 K. Preadsorbed CO inhibited the adsorption of NO on atop sites, whereas adsorption on hollow sites was not affected by the coexistence of CO. The adsorbed CO reacted with dissociated Oa and desorbed as CO2 at 574 K.     

An investigation on a broad infrared band with the maximum at approximately 1300 cm(-1) in magnesia cement,phase 3

In magnesia cement, phase 3, a broad and strong infrared band was observed with the maximum at approximately 1300 and 1050 cm(-1) in the H and D systems, respectively. To clarify the origin of the 1300 cm(-1) band the temperature dependency of the infrared spectra of the H system was observed and the spectra analyzed on the basis of a strong vibrational coupling of the OH stretching with lattice modes. The fitting was quite well, giving rise to the origin of the 1300 cm(-1) band of the OH stretching.     

Synthesis of optically active (+)-19-nortestosterone by asymmetric bis-annulation reaction

Michael reaction of 1,7-pctadien-3-one with 2-methylcyclopentane-1,3-dione, followed by intramolecular aldol condensation promoted by L-amino acids produced the optically active (+)-4-(3-butenyl)-7a-methyl-5,6,7,7a-tetrahydroindane-1,5-dione in high chemical and optical yields. The PdCl₂-catalyzed oxidation of the terminal double bond gave the methyl ketone, which had 76% optical purity and was made 100% optically pure by recrystallization. Then aldol condensation afforded the tricyclic ketone, which was alkylated with 3-butenyl iodide to afford (?)-3β-t-butoxy-2,3,3a,4,5,7,8,9,9aβ,9bα-decahydro-6-(3-butenyl)-3aβ-methyl-1H-benz[e]inden-7-one. The synthesis of this compound means the total synthesis of (+)-19-nortestosterone.