(Triisopropylsilyl)acetaldehyde acetal as a novel protective group for 1,2-diols

(Triisopropylsilyl)acetaldehyde dimethyl acetal (TIPS-ADMA) was synthesized from chlorotriisopropylsilane in three steps. Cyclic and acyclic 1,2-diols can be transformed to (triisopropylsilyl)ethylidene acetals (TIPS-AA). Removal of the acetal by LiBF₄ regenerates the starting diol in excellent yield even in the presence of an acetonide of 1,2-diol. The TIPS-AA group can survive under the deprotection conditions of the acetonide in acetic acid at 80 °C. Selective protection of 2,3- and 4,6-diols for O-methyl d-mannoside with TIPS-ADMA and selective deprotection of the acetals have been achieved.     

Studies on the syntheses of heterocyclic compounds. CLXXIV. An approach to the synthesis of oxyacanthine and berbamine

Schotten-Baumann reaction of the amine (X) with 4-benzyloxy-3,4′-oxydiphenylacetyl chloride (XI) gave two amides, (XIIa) and (XIIb), which were cyclized to give the corresponding 3,4-dihydroisoquinolines, respectively. Methylation of the above 3,4-dihydro-isoquinolines, followed by hydrolysis, afforded the compounds having the same composition as berbamine (Ia) and oxyacanthine (Ib), whose structures are under examination.     

Inhibitory effects of non-steroidal anti-inflammatory drugs on superoxide generation.

Effects of non-steroidal anti-inflammatory drugs (NSAID: amfenac sodium, diclofenac sodium, indomethacin and ketoprofen) on the generation of superoxide anion (O2-) by isolated rat polymorphonuclear leukocytes (PMN) were studied spectrophotometrically using cytochrome c. The effects of these drugs were also studied on O2- production by the xanthine-xanthine oxidase and reduced nicotinamide adenine dinucleotide phosphate (NADPH)-NADPH oxidase systems. Amfenac sodium, at 0.1 mM, inhibited significantly O2- generation in rat PMN induced by opsonized zymosan. At 0.5 mM, diclofenac sodium and indomethacin inhibited the O2- generation in rat PMN. All of the above drugs slightly inhibited O2- production by the xanthine-xanthine oxidase system. On the other hand, O2- production by the NADPH-NADPH oxidase system was significantly inhibited by the addition of amfenac sodium, ketoprofen or indomethacin. These results suggest that non-steroidal anti-inflammatory drugs do not work as an O2- scavenger and block O2- production by the NADPH-NADPH oxidase system of rat PMN. It is concluded that amfenac sodium and the other drugs are able to inhibit granulocyte O2- production by blocking the activation of NADPH-oxidase.     

Variation of free volume parameters of polyalkylmethacrylate derivatives in the range from 15 to 300 K probed by positron annihilation lifetime measurement

Positron annihilation lifetime measurements of PMMA, PEMA, PiPMA, PnPMA and PnBMA were performed in the temperature range between 15 and 300 K, where , and relaxational transitions occur for these polyalkylmethacrylates. The variations of free volume size and content calculated from the longest lifetime component against temperature are correlated to the results obtained by dielectric, viscoelastic and dynamic mechanical relaxation data of the polymers. The variations of free volume sizes and contents, apparent free volume fraction and size distribution of the polyalkylmethacrylates are well correlated with the rotational transitions of side chains. The location of free volumes, in which positronium annihilates can be estimated near the vicinity of alkyl groups bound to oxygen atom of side ester chains.     

Mössbauer and ESR study of the formation of phthalocyanineiron(II) pyridine adduct in the supercage of NaY,KY, and RbY zeolite

Phthalocyanineiron(II) (FePc) and phthalocyaninato[(2-)bispyridine]iron(II) (FePc(py)₂) synthesized in supercage of NaY, KY and RbY zeolite have been characterized by Mössbauer and ESR spectroscopy. The yield of formation of the pyridine adduct depends on the ionic radius of the alkali ions introduced into the supercage, but not on the number of iron ions trapped in the cages, suggesting that free space in the supercage was the most important factor for the formation of the FePc-py-adducts.     

A conducting crystal based on a single-component paramagnetic molecule, [Cu(dmdt)(2)] (dmdt = dimethyltetrathiafulvalenedithiolate)

A single-component conducting molecular crystal composed of paramagnetic copper complexes, [Cu(dmdt)2]0+, was prepared. The crystal has an unprecedented three-dimensionally packed molecular arrangement and exhibits a fairly high conductivity (1 S cm-1 at room temperature). The magnetic susceptibility measurements revealed that [Cu(dmdt)2]0+ molecule keeps most of S = 1/2 spin moments. The difference of the bond lengths between [Cu(dmdt)2]0+ and [Cu(dmdt)2]2- is consistent with the result of the molecular orbital calculation.