Study on radiation-induced polymerization of vinyl monomers adsorbed on inorganic substances. I. Radiation-induced polymerization of styrene adsorbed on several inorganic substances

The radiation-induced polymerization of styrene adsorbed on silica gel, white carbon, silicic acid anhydride, zeolite, and activated alumina was carried out to elucidate the effect of properties of inorganic substances on the polymerization. The rate of adsorbed state polymerization on these inorganic substances was very fast in comparison with that of bulk-state polymerization. The amount of unextractable polymer depends on the specific surface area and chemical compositions of these inorganic substances. Inorganic substances which contain aluminum as a component element are more likely to be grafted than those which consist of SiO₂ alone. The molecular weight and molecular weight distribution of unextractable polymer and extractable polymer differ from one another in each inorganic substance. In case of silicic acid anhydride, unextractable polymer has smaller molecular weight than extractable polymer. These results suggest that unextractable polymer cannot be extracted due to chemical bonds with the inorganic surface.     

Marstomentosides O-T polyoxypregnane glycosides from Marsdenia tomentosa

Thirteen pregnane glycosides were isolated from fresh leaves of Marsdenia tomentosa collected in the Fukuyama district. Of these, six were glycosides previously obtained from the same plant collected in the Fukuoka district and one from another Asclepiadaceous plant. The structures of the six new glycosides were determined by spectrometric method.     

Liquid-liquid extraction of copper(I) by cyclic tetrathio ethers

The liquid-liquid extraction of copper(I) with 12-, 13-, 15- and 16-membered cyclic tetrathio ethers ([n]aneS₄, where n represents the total number of carbon and sulphur atoms in the cyclic ligand ring) was examined stoichiometrically using picrate ion (Pic^?) for the formation of the ion pair. Copper(I) was extracted with four ligands (L) into 1,2-dichloroethane as the ion-pair compound, [Cu(I)L]⁺Pic^?. The extraction constant, K_ex, with each ligand was determined. As the ring size of cyclic tetrathio ethers increases, the log K_ex values, including that previously reported for [14]aneS₄, increase from 7.7 to 9.4. The value of Δ log K_ex, which represents the increase in log K_ex due to the addition of one carbon atom to the macrocyclic ring, was large between [13]aneS₄ and [14]aneS₄ (Δ log K_ex=1.0) and small between [14]aneS₄ and [15]aneS₄ (Δ log K_ex=0.1).     

220-MHz NMR spectra of acrylic monomer–2-substituted 1,3-diolefin alternating copolymers

An investigation by 220-MHz NMR spectroscopy was carried out on the alternating copolymers of acrylic monomer with 2-substituted 1,3-diolefin. The chain structures were determined. The acrylic monomers used were methyl methacrylate (MMA), acrylonitrile (AN), and methacrylonitrile (MAN); isoprene (IP) and chloroprene (CLP) were the 1,3-diolefins. In the MAN–IP alternating copolymer, the 1-position methylene protons of IP showed an AB quartet peak, confirming the α-1 linkage structure. Similarly, in the MMA–CLP and AN–CLP copolymers, the 1-position methylene protons of CLP showed and AB quartet and an ABX pattern, respectively, confirming the α-1 linkage structure in both these cases also. The α-1 linkage structure was also revealed by the decoupling technique in the MAN–CLP alternating copolymer. The AN–IP and MMA–IP alternating copolymers also possess a bond between the α-position of the acrylic monomer and the 1-position of IP. The monomeric units in the alternating copolymers of acrylic monomers with 2-substituted 1,3-diolefins were generally linked at the α-position of acrylic monomer and the 1-position of 1,3-diolefin. On the other hand, in the Diels-Alder adducts of acrylic monomer with 2-substituted 1,3-diolefin, the reaction takes place between the α-position of acrylic monomer and the 4-position of 1,3-diolefin. The regioselectivity of the alternating copolymers and the Diels-Alder adducts is quite compatible with the expectations from molecular orbital theory.     

Plaunol A and B,new anti-ulcer diterpenelactones from Crotonsublyratus

Two new diterpenelactones named plaunol A ($\text{2}$) and B ($\text{3}$) exhibiting anti-Shay ulcer activity were isolated from Thai medicinal plant, $\text{Croton}$$\text{sublyratus}$. Structure of $\text{2}$ was determined by X-ray analysis of its $\text{p}$-bromobenzoate and structure of $\text{3}$ was deduced from the results of chemical correlation and the spectral data.     

Chlorovulones,new halogenated marine prostanoids with an antitumor activity from the stolonifer clavularia viridis Quoy and Gaimard

New halogenated marine prostanoids, chlorovulone I, II and III were isolated from the stolonifer $\text{Clavularia}$$\text{viridis}$ Quoy and Gaimard. The structure elucidation and the antitumor activity of chlorovulones were described.     

Regioselective oxygenative tetraamination of [60]fullerene. Fullerene-mediated reduction of molecular oxygen by amine via ground state single electron transfer in dimethyl sulfoxide

The reaction of [60]fullerene with a variety of a secondary aliphatic amines in 20% v/v dimethyl sulfoxide in chlorobenzene under an atmospheric pressure of molecular oxygen allows regioselective introduction of four amino groups and one epoxide group around one pentagon of the fullerene molecule in good to high yield. This new synthesis of tetraaminofullerene expoxide can be carried out with a simple procedure on a multigram scale at room temperature and affords a variety of functionalized fullerene derivatives. Near-infrared analysis of a mixture of [60]fullerene and piperidine in a deaerated dimethyl sulfoxide/chlorobenzene mixture indicated equilibrium formation of [60]fullerene radical anion (C60*-) that persists at least for 2 weeks at room temperature but reacts immediately with molecular oxygen to give the tetraaminofullerene expoxide. The Benesi-Hildebrand analysis of the concentration dependency of the near-infrared absorption indicated that a [C60*- piperidine*+] radical ion pair is formed with an equivalent constant of K = 0.62 +/- 0.02 M(-1) at 25 degrees C. This and other lines of evidence suggest that the oxygenative amination reaction involves C60-mediated reduction of molecular oxygen by the amine.     

An efficient 1,3-dipolar cycloaddition between aromatic selenoaldehydes and nitrile oxides or nitrile imines: an easy access to selenium-containing five-membered heterocyclic ring system

1,3-Dipolar cycloaddition between aromatic selenoaldehydes, generated by thermal retro Diels-Alder reaction of anthracene cycloadducts, and nitrile oxides or nitrile imines proceeded efficiently to give the corresponding [3+2] cycloadducts as a single isomer in good yields, being 1,4,2-oxaselenazoles or 1,3,4-selenadiazoles, respectively.