Facile preparation of organozinc bromides using electrogenerated highly reactive zinc and its use in cross-coupling reaction

Highly reactive zinc was readily prepared by electrolysis of a DMF solution containing pyrene as a mediator with a platinum cathode and a zinc anode. Preferential reduction of pyrene occurred to generate the corresponding radical anion, which reduced zinc ions generated from anodic dissolution to give zero valent zinc with high reactivity. The reactive zinc was successfully used for an efficient transformation of bromoalkanes into the corresponding organozinc bromides. Organozinc bromides obtained were further used successfully in Pd-catalyzed cross-coupling reaction with various aryl iodides and bromides.     

Oesophageal cancer treated by photodynamic therapy alone or followed by radiation therapy

Photodynamic therapy (PDT) with porphyrins and red light is receiving increasing attention in the management of malignant tumours. At present PDT is primarily indicated for the treatment of superficial or early-stage lesions. At the Department of Radiotherapy and the First Institute of Surgery in Padova (Italy) more than 150 cases of tumours of different types have been treated using this technique. This paper briefly describes 21 cases of superficial oesophageal cancer. A complete response was observed in 11 of 21 cases. Radiation therapy appeared to be very effective as a salvage treatment of non-response patients.     

SYNTHESIS OF ORGANOGERMANE OLIGOMERS VIA LIGAND SUBSTITUTION POLYMERIZATION FROM 1, 4-DIOXANE COMPLEX OF GERMANIUM DICHLORIDE

Some organogermanium oligomers with different side groups were synthesized via li-gand substitution polymerization from 1, 4-dioxane complex of germanium dichloride withdifferent organolithitum compounds. The oligomers were isolated through either precipi-tation from methanol or extraction using toluene with a yield of no less than 50%. Theweiglit average molecular weight (M_w) of the oligomers is ranging from 1.4×10~3 to 5.9×10~3depending on the type and alkyl length of the organolithium compounds used.     

Reaction of 3,4-disubstituted 1,2,5-oxadiazole 2-oxides with dipolarophiles : Substituent and solvent effect on the reaction courses

A variety of symmetrically or unsymmetrically 3,4-disubstituttd furoxans such as dicyano, dialkyl, diacyl, bis(phenylsulfonyl), N.N'-dialkyldicarbamoyl, 3(or 4)-methyl-4(or -3)-phenyl(or nitro, ethoxy, phenoxy, phenylthio, pyrrolidinyl, phenylsulfonyl), 3(or 4)-ethyl-4(or -3)phcnyl, and 3(or 4)-ethoxy-4(or -3)-phenylsulfonylruroxan reacted with dipolarophiles in toluene or xylene at the refluxing temperature to give nitrone-type 1,3-dipolar cycloadducts, 5-substituted 1-aza-2,8-dioxabicyclo-[3.3.0]octanes and/or 3-substituted 2-isoxazoline 2-oxides. On the other hand, some of the furoxans gave 2-isoxazolines via nitrile oxide 1,3-dipolar cycloaddition in a toluene (or xylene)-DMF solvent at the refluxing temperature.     

Partially bio‐based tri‐ and hexaallyl monomers: Synthesis from naturally occurring myo‐inositol and polyaddition with dithiols

myo‐Inositol, a naturally occurring cyclic hexaol, was converted to 2,4,6‐tri‐O‐allyl‐myo‐inositol and 1,2,3,4,5,6‐hexa‐O‐allyl‐myo‐inositol. Polyaddition of the former product, a tri(allyl ether) bearing three hydroxyl groups, with dithiols yielded the corresponding networked polymers. Their glass transition temperatures (T_gs) were higher than those of networked polymers formed by the polyaddition of 1,3,5‐tri‐O‐methyl‐2,4,6‐tri‐O‐allyl‐myo‐inositol. This implied the reinforcement of the networks by hydrogen bonding between the hydroxyl groups. Polyaddition of the latter product, a hexa(allyl ether), with dithiols yielded the corresponding networked polymers with much higher T_gs than those of all of the aforementioned networked polymers. This implied that efficient use of the hexafunctional monomer leads to the formation of more densely crosslinked polymers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1524–1529     

Discovery of radioactive silver (110mAg) in spiders and other fauna in the terrestrial environment after the meltdown of Fukushima Dai-ichi nuclear power plant

Six months after the explosion of TEPCO’s Fukushima Dai-ichi nuclear power plant, radioactive silver (^110mAg), was detected in concentrations of 3754 Bq/kg in Nephila clavata (the orb-web spider; Joro-gumo in Japanese) collected at Nimaibashi, Iitate village in Fukushima Prefecture, whereas ^110mAg in the soil was 43.1 Bq/kg. A survey of 35 faunal species in the terrestrial environment during the 3.5 years after the accident showed that most of Anthropoda had two orders higher ^110mAg in their tissues than soils, although silver is not an essential element for their life. However, tracing of the activity of ^110mAg detected in spider Atypus karschi collected regularly at a fixed location showed that it declined much faster than the physical half-life. These results suggest that ^110mAg was at once biologically concentrated by faunal species, especially Arthropoda, through food chain. The factors affecting the subsequent rapid decline of ^110mAg concentration in faunal species are discussed.     

Regio-specific total synthesis of (±)-2-hydroxyaklavinone

The tricyclic quinone 8 was successfully synthesized from naphthazalin, and the total synthesis of (±)-2-hydroxyaklavinone via 8 was accomplished in an overall yield of about 18% through the regio-controlled route.     

Pion-distribution amplitude within the instanton model

The leading-twist pion-distribution amplitude is obtained at a low normalization scale of order ρ _c (inverse average size of an instanton). Pion dynamics, consistent with gauge invariance and low-energy theorems, is considered within the instanton vacuum model. The results are QCD-evolved to higher momentum-transfer values and are in agreement with recent data from CLEO on the pion transition form factor. It is also shown that some previous calculations violate the axial Ward-Takahashi identity.     

A modified technique of the self-absorption method applicable to natural mercury afterglows

A modified technique of the self-absorption method has been developed and applied to natural mercury afterglows. A narrow light-emitting layer is produced inside an absorption tube by external pumping at the moment of measuring the afterglow.