Syntheses of apogalanthamine analogs as α-adrenergic blocking agents. IX. Syntheses of optically active 8-hydroxy-6-methyl-5,6,7,8-tetrahydrodibenz[c,e]azocines

(8R) and (8S)-Hydroxy-6-methyl-5,6,7,8-tetrahydrodibenz[c,e]azocines (R- and S- 1 ) were synthesized by oxidative kinetic resolution of N-(2-iodobenzyl)-β-(2-iodophenyl)ethanolamine ( 8 ), followed by cyclization of the optically active acetates (R- and S- 6 ) of R- and S- 8 with zero-valent nickel to (8R)- and (8S)-acetoxyazocines (R- and S- 7 ), and by hydrolysis of the acetates ( R - and S- 7 ).     

Selective Ni-P electroless plating on photopatterned cationic adsorption films influenced by alkyl chain lengths of polyelectrolyte adsorbates and additive surfactants

We demonstrated that the photopatterned single-layer adsorption film of poly(1-dodecyl-4-pyridinium bromide) on a silica surface was available for a template of nickel-phosphorus (Ni-P) electroless plating through sensitization with a SnCl(2) aqueous solution and activation with a PdCl(2) aqueous solution. Four kinds of poly(1-alkyl-4-vinylpyridinium halide)s bearing methyl, propyl, hexyl, and dodecyl groups were prepared. The cationic polymers were adsorbed by a negatively charged silica surface from their solutions, to form single-layer adsorption films exhibiting desorption-resistance toward deionized water and ethanol. The organic adsorption films could be decomposed completely by exposure to 172 nm deep-UV light. The formation and decomposition of the single-layer films were confirmed by deep-UV absorption spectral measurement and zeta-potential measurement. Ni-P electroless plating was carried out on the photopatterned adsorption films, using three types of SnO(x) colloidal materials without and with cationic or anionic surfactant as catalyst precursors in the sensitization step. In the case of the negatively charged SnO(x) colloids surrounded by anionic surfactant, Ni-deposition took place preferentially on the cationic adsorption films remaining in unexposed regions. The Ni-deposition was accelerated significantly on the cationic adsorption film bearing dodecyl groups. It was obvious by ICP-AES analyses that the hydrophobic long-chain dodecyl groups in the adsorption film could promote the adsorption of the negative SnO(x) colloids on the film surface, followed by much nucleus formation of zerovalent Pd catalysts useful for the electroless plating. The result of our experiment clearly showed that, in addition to electrostatic interaction, van der Waals interaction generating between the hydrophobic long-chain hydrocarbons of the adsorption film and the surfactant improved significantly the adsorption stability of the SnO(x) colloids, resulting in highly selective Ni-deposition in accord with the photopattern shape of the cationic single-layer adsorption film.     

Modification of poly(vinyl chloride). XXXI. Crosslinking of poly(vinyl chloride) with 2-R-4,6-dithiol-s-triazine and metal activators

Crosslinking of poly(vinyl chloride) (PVC) with 2-R-4,6-dithiol-s-triazine (R-DT) and metal activators has been studied to determine crosslinking rate constants, induction periods, and apparent activation energy and the final efficiency of crosslinking agents. The rate constants were about 1.4–7.5 min^?1 and the induction periods were about 6.8–24.3 min for various kinds of R-DT at 180°C. The activation energy was about 16.6–33 kcal/mol over the temperature range 160–195°C. The rate constants were strongly influenced by 2-substituted groups (R) in R-DT and increased in the order R′O-? R′NH-< (R′)₂N, where R′ is an alkyl or aryl group. Further, the rate constants increased in the order of: metal carboxylates < metal carboxylates < metal oxides for the activators and in the order of: Pb < Mg < Ca < Ba < Na for metal atoms. The final efficiency was about 75–80% for the activators such as MgO, MgCO₃, PbO, and SnO. The activators containing Na, Ca, and Ba atoms, however, gave final efficiency of more than 100%.     

Thermal decomposition mechanisms of tert-alkyl peroxypivalates studied by the nitroxide radical trapping technique

The thermolysis of a series of tert-alkyl peroxypivalates 1 in cumene has been investigated by using the nitroxide radical-trapping technique. tert-Alkoxyl radicals generated from the thermolysis underwent the unimolecular reactions, beta-scission, and 1,5-H shift, competing with hydrogen abstraction from cumene. The absolute rate constants for beta-scission of tert-alkoxyl radicals, which vary over 4 orders of magnitude, indicate the vastly different behavior of alkoxyl radicals. However, the radical generation efficiencies of 1 varied only slightly, from 53 (R = Me) to 63% (R = Bu(t)()), supporting a mechanism involving concerted two-bond scission within the solvent cage to generate the tert-butyl radical, CO(2), and an alkoxyl radical. The thermolysis rate constants of tert-alkyl peroxypivalates 1 were influenced by both inductive and steric effects [Taft-Ingold equation, log(rel k(d)) = (0.97 +/- 0. 14)Sigmasigma - (0.31 +/- 0.04)SigmaE(s)(c), was obtained].     

Photocyclisierungen von 1, 1'-Polymethylen-di-2-pyridonen. 46. Mitteilung über Photoreaktionen

Photocyclization of 1, 1′-Polymethylene-di-2-pyridones . Benzophenone sensitized irradiation of the four dipyridones 1-4 gave the internal photocyclization products 6 (64%, Scheme 4), 7 (60%, Scheme 5), 8 (Scheme 6), and 11 (26%, Scheme 7), respectively. The decamethylene compound 5 yielded only polymeric material. The primary [2+2] photoproduct 8 from dipyridone 3 (Scheme 6) is relatively unstable. Further irradiation or heating to 65° induced a Cope rearrangement to give compound 9 which, on heating to 137°, was converted into the isomeric compound 10 . This product, as well as the other photoproducts mentioned, are rearranged back to their respective starting materials upon direct irradiation with 254 nm light or by heating to higher temperatures. The various possibilities for cycloadditions of pyridones are discussed as well as the possible factors which are responsible for the highly regioselective photoreactions of the dipyridones 1–4 .     

Controlling the incorporation and release of C60 in nanometer-scale hollow spaces inside single-wall carbon nanohorns

We succeeded in large-scale preparation of single-wall carbon nanohorns (SWNH) encapsulating C60 molecules in a liquid phase at room temperature using a "nano-precipitation" method, that is, complete evaporation of the toluene from a C60-SWNH-toluene mixture. The C60 molecules were found to occupy 6-36% of the hollow space inside the SWNH, depending on the initial quantity of C60. We showed that the C60 in C60@SWNHox was quickly released in toluene, and the release rate decreased by adding ethanol to toluene. Numerical analysis of the release profiles indicated that there were fast and slow release processes. We consider that the incorporation quantity and the release rate of C60 were controllable in/from SWNHs because SWNHs have large diameters, 2-5 nm.     

Reactions of methylenecyclopropanes with a diethylzinc-bromoform system, and the utilization for synthesis of a novel cyclopropylidene-nucleoside

The reactions of substituted methylenecyclopropane with diethylzinc-bromoform gave bromospiro[2.2]pentane derivatives, bromoform-addition compounds, an oxabicyclo-compound and adjacent dibromo-compound, and the last product was derived to a novel ,β-unsaturated nucloside.     

Zooxanthellamide A, a novel polyhydroxy metabolite from a marine dinoflagellate of Symbiodinium sp.

A novel polyhydroxy metabolite named Zooxanthellamide A, C₁₂₈H₂₂₂N₂O₅₄S₂, was isolated from a cultured marine dinoflagellate, Symbiodinium sp., and the chemical structure was determined by spectroscopic methods.     

Saccharification and alcohol fermentation in starch solution of steam-exploded potato

Steam explosion pretreatment of potato for the efficient production of alcohol was experimentally studied. The amount of water-soluble starch increased with the increase of steam pressure, but the amounts of methanol-soluble material and Klason lignin remained insignificant, regardless of steam pressure. The potatoes exploded at high pressure were hydrolyzed into a low molecular liquid starch, and then easily converted into ethanol by simultaneous saccharification and fermentation using mixed microorganisms: an amylolytic microorganism,Aspergillus awamori, and a fermentation microorganism,Saccharomyces cerevisiae. The maximal ethanol concentration was 4.2 g/L in a batch culture at 15 g/L starch concentration, and 3.6 g/L in a continuous culture fed the same starch concentration. In the fed-batch culture, the maximal ethanol concentration increased more than twofold, compared to the batch culture.