A Novel Reactivity of Phosphanylalumane (>P−Al<): Reversible Addition of a Saturated Interelement Bond to Olefins

The reversible addition of olefins to a phosphanylalumane, P−Al single-bond species, was investigated. The P−Al bond added to ethylene and relatively small terminal alkenes (propylene and hex-1-ene) at room temperature to give the corresponding alkene adducts. Heating the terminal alkene adducts released the corresponding alkenes and regenerated the P−Al bond, but no release of ethylene was observed even under vacuum conditions. The reactivity of ethylene adduct as a new saturated C₂ vicinal P/Al-based FLP was also investigated. The ethylene adduct was found to undergo complexation with nitriles to give the corresponding nitrile adducts to the Al center, which retained the ethylene tether as in the case of the corresponding P/B-based FLP. However, the reactivity of ethylene toward CO₂ and benzaldehyde differed from that of the P/B system giving the corresponding adducts.     

Alternating copolymers of hexafluoroisobutylene with vinyl trifluoroacetate and vinyl pentafluorobenzoate

Copolymerizations of hexafluoroisobutylene (HFIB) with vinyl pentafluorobenzoate (VPFB) and vinyl trifluoroacetate (VTFA) were carried out in bulk using perfluorodibenzoyl peroxide as the radical initiator. The copolymers obtained were characterized by proton and fluorine NMR spectroscopy. The monomer reactivity ratios in the polymerization of HFIB with VPFB were r₁ (HFIB) = 0, r₂ (VPFB) = 0.373, and r₁r₂ = 0. The results indicated that these copolymers have alternating structures. Similarly, the copolymers of HFIB and VTFA also showed alternating structures. The films of HFIB‐co‐VPFB were prepared by casting THF solution of polymers. Films obtained were flexible and transparent. The refractive indices of copolymers were 1.4549, 1.4490, and 1.4438 at 532, 633, and 839 nm, respectively. The average T_gs of HFIB‐co‐VTFA and HFIB‐co‐VPFB were 52 and 71 °C, respectively. From these results, the T_g of the hypothetical HFIB homopolymer is postulated to be in between 70 and 90 °C, which may be useful in the assessment of T_gs of HFIB copolymers with other vinyl monomers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Numerical study of QCD phase diagram at high temperature and density by a histogram method

We study the QCD phase structure at high temperature and density adopting a histogram method. Because the quark determinant is complex at finite density, the Monte-Carlo method cannot be applied directly. We use a reweighting method and try to solve the problems which arise in the reweighting method, i.e. the sign problem and the overlap problem. We discuss the chemical potential dependence of the probability distribution function in the heavy quark mass region and examine the applicability of the approach in the light quark region.     

Oxygen bridged Homobinuclear Mn(II) compounds with Anthranilic acid: Theoretical calculations,oxidation and catalase activity

Two new homobinuclear manganese compounds with mixed ligands, [Mn₂(μ_1,1–2‐NH₂C₆H₄COO)₂(phen)₄](ClO₄)2(CH₃OH) ( 1 ), and [Mn₂(μ_1,3–2‐NH₂C₆H₄COO)₂(bipy)₄](ClO₄)2 ( 2 ) (NH₂C₆H₄COOH = anthranilic acid, bipy = 2,2′‐bipyridine, phen = 1,10‐ phenanthroline) were synthesized and thoroughly characterized by elemental analysis, IR, UV and single crystal X‐ray crystallography. X‐ray structure analysis shows that in the mono‐ and bidentate carboxylate bridged compounds, Mn–Mn distances of 1 and 2 are 3,461 Å, and 4,639 Å, respectively. The energy of the compounds was determined with a DFT (Density Functional Theory) calculation on B3LYP/6‐31G(d,p) optimized geometry by using the B3LYP/6‐31G(d,p) basis set. These compounds acts as biomimetic catalyst and show catalase‐like activity for the hydrogen peroxide dismutation at room temperature in different solvents with remarkable activity (TOF, Turnover frequency = mol of subst./(mol of cat. × time)) up to 12640 h^?1 with 1 , and 17910 h^?1 with 2 in Tris–HCl buffer). Moreover, the catalytic activity of 1 and 2 has been studied for oxidation of alcohols (cinnamyl alcohol, benzyl alcohol, cyclohexanol, 1‐octanol and 1‐heptanol) and alkenes (cyclohexene, styrene, ethyl benzene, 1‐octene and 1‐hexene) in a homogeneous catalytic system consisting t‐butylhydroperoxide (TBHP) as an oxidant in acetonitrile. Both compounds exhibited very high activity in the oxidation of cyclohexene to cyclohexanone (~80% selectivity, ~99% conversion in 1 h, TOF = 243 h^?1 and 226 h^?1) and cinnamyl alcohol to cinnamaldehyde (~64% selectivity) as the main product with very high TOF value (9180 h^?1 and 13040 h^?1 in the first minute of reaction) (~100% conversion in 0.5 h) with TBHP at 70 °C in acetonitrile, for 1 and 2 , respectively.     

Separation and purification of 99mTc from 99Mo produced by electron linear accelerator

The medical radionuclide ⁹⁹Mo was produced by the ¹⁰⁰Mo(γ,n) reaction using bremsstrahlung photons generated by an electron linear accelerator. The amount of ⁹⁹Mo produced was compared to that predicted by calculation using the particles and heavy ion transport code system. From the ⁹⁹Mo produced, highly pure ^99mTc was separated using the so-called technetium master milker, and the chemical yield of ^99mTc was 83–99 %. The installation of a new complex using this method and the electron linear accelerator with the preferable specification was suggested, and a possibility to supply the demand of ^99mTc was discussed and shown.

     

REACTION OF SULFUR CHLORIDE WITH ACETOPHENONE. II

Abstract

In a previous paper,¹ we reported the formation of a resinous material (1) from the reaction of sulfur chloride with acetophenone which, upon treatment with DMF, yielded phenylglyoxylthiodimethylamide (4). We now report two additional resinous materials (5, 6), resulting from bromination of sodium phenacylthiosulfate (3) and diphenacyl disulfide (7) respectively, both of which not only resemble resinous 1 in appearance, but also yield 4 upon treatment with DMF in aqueous alkali.

Resinous 1, 5, and 6 appear to have the same common basic structure and differ only in the number of sulfur atoms bonded between the common units. Cleavage at the sulfur-sulfur bonds and elimination of hydrogen halide then yields identical oxothioamides from 1, 5, or 6. The latter appears to be a general reaction, and several oxothioamides were prepared by this synthetic method from 1, 5, and 6 and various amides and amines.