Thermolysis of reactive oligo(p-phenylene sulfide) containing disulfide bond

Oligo(phenylene sulfide) (OPS) containing one disulfide bond at the end of the chain, which was obtained by the oxidative polymerization of diphenyl disulfide, had a relatively low Td_10%(temperature for 10% weight loss) of 412 °C because of degradation of the disulfide bond. But this thermal cleavage of the disulfide bond promoted the curing reaction through thiophenoxy radical formation. OPS was allowed to react with diiodobenzene at 220 °C. The thermal stability of OPS was improved through the consumption of the disulfide bond and the coupling of the chain.     

On the correlation between NQR frequency and bond length in I3−

A linear correlation between the NQR frequency of the terminal iodine atom and the corresponding I-I bond length in I₃^? was found in several compounds containing triiodide anions. A simple extended Huckel MO calculation suggested that such a correlation can be used to check the validity of wavefunctions of iodine.     

Radiocarbon dating of an ancient Japanese document “Minamoto no Yoritomo Sodehan Migyosho” by accelerator mass spectrometry

We measured radiocarbon age of an ancient document “Minamoto no Yoritomo Sodehan Migyosho”. The content tells that it was issued in 1189 by “Minamoto no Yoritomo” known as the virtually first shogun in Japan to grant “Matsugi” family the privilege of controlling craftsmen of foundry industry. Paleographical views, however, suggested that it can be a counterfeit. The radiocarbon dating clarified that the document was written not in the 12th but after the 16th century.     

The chemical synthesis of a cyclic oligosaccharide derivative with branching

A cyclic oligosaccharide derivative was synthesized by cationic ring-opening polymerization of an anhydrodisaccharide derivative under high vacuum in dichloromethane with 20 mol% of PF₅ as initiator. Analysis of the spectral results showed that the oligomer chain is composed of only 3 glucose units connected by -1,6 linkages with a glucopyranosyl branching unit at C-4 of each sugar residue in the main chain.     

Intramolecular photoreactions of 6-(ω-alkenyl)-4-methoxy-2-pyrones

6-(ω-Alkenyl)-2-pyrones 3a-c and 8a, b were prepared and the photochemical reactions were investigated. Photosensitized reactions of 3b, c gave intramolecular [2+2]-cycloadducts 11b, c as tricyclic lactones, site-and regio-specifically. They are not frontier-orbital-controlled adducts. On the other hand, 3a, 8a, b afforded cyclobutenecarboxylic acids, 10a, 14a, b , respectively. The end-ester group at the side-chain is thought not to be effective for the intramolecular phptoaddition.     

Synthesis and metal-ion binding properties of monoazathiacrown ethers

Synthetic procedures for monoazathiacrown ethers were explored, and monoazatrithia-12-crown-4, monoazatetrathia-15-crown-5, and monoazapentathia-18-crown-6 were obtained in moderate yields by the reaction of bis(2-chloroethyl)amine with the appropriate dithiols in the presence of lithium hydroxide in THF. To evaluate metal-ion binding properties of the monoazathiacrown ethers by solvent extraction, lipophilic dodecyl and dodecanoyl groups were incorporated onto the monoazathiacrown ethers. The solvent extraction experiments suggested that monoazathiacrown ethers have Ag(+) and Hg(2+) selectivities and that the relative selectivity between Ag(+) and Hg(2+) depends on their nitrogen atom properties and numbers of sulfur atoms reflecting the respective affinities of nitrogen and sulfur atoms to Hg(2+) and Ag(+). An interesting ability to bind Mg(2+) was observed in the case of N-dodecyl monoazatrithia-12-crown-4.