Triethylborane-induced radical allylation reaction with zirconocene-olefin complex

[reaction: see text] Allylzirconium reagents are effective for radical allylation of alpha-halo carbonyl compounds. The key steps would be homolytic cleavage of the zirconium-carbon bond and halogen abstraction by the resulting Cp(2)ZrCl(III). Zirconocene-olefin complex can be also utilized for the allylation of alpha-halo compounds.     

Cobalt-catalyzed Heck-type reaction of alkyl halides with styrenes

A cobalt complex, CoCl2[1,6-bis(diphenylphosphino)hexane], catalyzes an alkylation reaction of styrenes in the presence of Me3SiCH2MgCl in ether to yield beta-alkylstyrenes. A variety of alkyl halides including alkyl chlorides can be employed as an alkyl source. A radical mechanism is strongly suggested for this alkylation reaction.     

Adsorption Characteristics of Pb(II) and Cr(III) onto C‐4‐Methoxyphenylcalix[4]Resorcinarene in Batch and Fixed Bed Column Systems

A study on the adsorption characteristics of Pb(II) and Cr(III) cations onto C‐4‐methoxyphenylcalix‐[4]resorcinarene (CMPCR) in batch and fixed bed column systems has been conducted. CMPCR was produced by one step synthesis from resorcinol, 4‐methoxybenzaldehyde, and HCl. The synthesis was carried out at 78 °C for 24 hours and afforded the adsorbent in 85.7% as a 3:2 mixture of C_4ν:C_2ν isomer. Most parameters in batch and fixed bed column systems confirm that CMPCR is a good adsorbent for Pb(II) and Cr(III), though Pb(II) adsorption was more favorable than that of Cr(III). The adsorption kinetic of Pb(II) and Cr(III) adsorptions in batch and fixed bed column systems followed a pseudo 2ⁿ order kinetics model. The rate constant of Pb(II) was higher than that of Cr(III) in the batch system, but this result was contrary to the result obtained in a fixed bed column system. Desorption studies to recover the adsorbed Pb(II) and Cr(III) were performed sequentially with distilled water and HCl, and the results showed that the adsorption was dominated by chemisorption.     

Synthesis,Properties, and Redox Behavior of 1,1,4,4‐Tetracyano‐2‐ferrocenyl‐1,3‐butadienes Connected by Aryl,Biaryl, and Teraryl Spacers

Aryl‐substituted 1,1,4,4‐tetracyano‐1,3‐butadienes (FcTCBDs) and bis(1,1,4,4‐tetracyanobutadiene)s (bis‐FcTCBDs), possessing a ferrocenyl group on each terminal, were prepared by the reaction of a variety of alkynes with tetracyanoethylene (TCNE) in a [2+2] cycloaddition reaction, followed by retro‐electrocyclization of the initially formed [2+2] cycloadducts (i.e., cyclobutene derivatives). The characteristic intramolecular charge transfer (ICT) between the donor (ferrocene) and acceptor (TCBD) moieties were investigated by using UV/Vis spectroscopy. The redox behaviors of FcTCBDs and bis‐FcTCBDs were examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their properties of multi‐electron transfer depending on the number of ferrocene and TCBD moieties. Moreover, significant color changes were observed by visible spectroscopy under the electrochemical reduction conditions.     

Introduction of multiple γ-ray detection to charged particle activation analysis

Charged particle activation analysis (CPAA) is a rapid method with high accuracy which can analyze multi-elements simultaneously. Since multiple γ-ray detection method is expected to improve the detection efficiency and the signal-to-noise ratio, we study what design of the γ-ray detector array is the most suitable for CPAA. We take up four design candidates and investigated the responses by the radiation simulation code Geant 4. From the results, we have deduced the best design with 5 germanium detectors in close geometry. By inspecting the sensitivity in CPAA, the method is proved to be useful and applicable to 116 nuclides.

     

On Partitional Labelings of Graphs

The notion of partitional graphs, a subclass of sequential graphs, is introduced, and the cartesian product of a partitional graph and K ₂ is shown to be partitional. Every sequential graph is harmonious and felicitous. The partitional property of some bipartite graphs including the n-dimensional cube Q _n is studied, and thus this paper extends what was known about the sequentialness, harmoniousness and felicitousness of such graphs.     

Radiation-Induced Polymerization of Tetrafluoroethylene

Polymerization of tetrafluoroethylene was carried out in bulk at low temperatures by initiation with γ-rays from a ⁶⁰ Co source. It was found that a remarkable postpolymerization takes place even in the liquid phase. Kinetical analysis has been made of the in-source and postpolymerizations. An activation energy of 2.7 kcal/mole was obtained for the in-source polymerization and 10.3 kcal/mole for the postpolymerization. The long lifetime of polymer radicals in the liquid phase at -78°C seems to be due to the slow recombination rate of the polymer radicals, based on the rodlike shape of the polymer radicals.     

Iron‐ and Bismuth‐Catalyzed Asymmetric Mukaiyama Aldol Reactions in Aqueous Media

We have developed asymmetric Mukaiyama aldol reactions of silicon enolates with aldehydes catalyzed by chiral Fe^II and Bi^III complexes. Although previous reactions often required relatively harsh conditions, such as strictly anhydrous conditions, very low temperatures (?78 °C), etc., the reactions reported herein proceeded in the presence of water at 0 °C. To find appropriate chiral water‐compatible Lewis acids for the Mukaiyama aldol reaction, many Lewis acids were screened in combination with chiral bipyridine L1 , which had previously been found to be a suitable chiral ligand in aqueous media. Three types of chiral catalysts that consisted of a Fe^II or Bi^III metal salt, a chiral ligand ( L1 ), and an additive have been discovered and a wide variety of substrates (silicon enolates and aldehydes) reacted to afford the desired aldol products in high yields with high diastereo‐ and enantioselectivities through an appropriate selection of one of the three catalytic systems. Mechanistic studies elucidated the coordination environments around the Fe^II and Bi^III centers and the effect of additives on the chiral catalysis. Notably, both Brønsted acids and bases worked as efficient additives in the Fe^II‐catalyzed reactions. The assumed catalytic cycle and transition states indicated important roles of water in these efficient asymmetric Mukaiyama aldol reactions in aqueous media with the broadly applicable and versatile catalytic systems.