Permeability to oxygen of poly(methyl methacrylate) films containing silane-treated glass flakes

Permeability to oxygen of poly(methyl methacrylate) (PMMA) films containing glass flakes (GF) was investigated. The glass flakes were treated with five kinds of silanes and K₂Cr₂O₇-H₂SO₄ solution to improve the affinity with PMMA. The permeability curves were classified into five representative types, which depend on the pretreatment of the glass flakes and the type of silane used as a coupling agent. The factors which influence permeability were studied from the point of view of permeative retardation with the aid of several methods, such as determination of the apparent density of the glass flakes treated with the silanes, the shearing and tensile strength of the PMMA films containing the glass flakes, ESR spectra of films irradiated by γ-rays, and x-ray diffraction patterns of the films. It was found that the three very effective methods to retard the permeability are (a) pretreatment of the glass flakes with NaOH, (b) treatment with γ-methacryloxypropyltrimethoxysilane or ditrimethylsiloxymethylsilane, and (c) heat pressing of the films. The lowest permeability constant which was attained in this study was about one-eighth that with PMMA alone.     

A new synthesis of olefins. Conversion of nitroolefins into olefins by reductive elimination

A nitro group in nitroolefins is displaced by hydrogen giving the corresponding olefins in good yields by the reaction of nitroolefins with sodium sulfide in the presence of benzenethiol. It proceeds rapidly at room temperature.     

Benzolactams. II. Synthesis of tetrahydrobenz[d]indeno-[1,2-b]azepines and their 12-Oxo derivatives

Aromatic methoxy and/or methylenedioxy substituted 7-methyltetrahydrobenz[d]indeno[1,2-b]-azepines 7 and their 12-oxo derivatives 8 were efficiently synthesized by the general method consisting of two types of intramolecular dehydrative cyclizations, as follows. N-Methyl-N-β-phenethylacetamides 1 were cyanomethylated in the two-step process of chloromethylation and treatment of the resultant benzyl chlorides with sodium cyanide. The condensation of the benzyl cyanides 2 with the appropriate benzaldehydes, followed by reduction of the benzylidene function, gave α,β-diphenylpropionitriles 3 . Successively, hydrolysis to the amino acids 4 and the thermal cyclization converted 3 to the benzylbenzazepinones 5 , which were also prepared by benzylation of the benzazepinones 6 smoothly by heating of 5 with phosphoryl chloride to afford the title azepines 7 . Further, these tetracyclic enamines 7 underwent autoxidation to the corresponding 12-oxo derivatives 8 , on exposure to oxygen in the presence of Triton B.     

Synthesis and complexation of a novel cyclophane

A novel cyclophane, 17, 17, 40, 40-tetramethyl-7, 30-dinitro-1, 10, 24, 33-tetraoxa[2.2.1.2.2.1] metaparaparametaparaparacyclophane, was synthesized by 2:2 cyclization of 3,5-bis(bromomethyl)nitrobenzene, derived from 3,5-dimethylnitrobenzene, and bisphenol A. The cyclophane was found to form 1:1 complex with benzene.     

X-ray and IR studies on crystal and molecular structure of 4-nitro-2,6-diphenylphenol. Stereochemistry of bifurcated OH⋯π hydrogen bonds

The crystals of the title compound contain both intra- and inter-molecular OH?π hydrogen bonds (the first example of bifurcated OH?π bonds), the stereochemistry of which has been elucidated by an X-ray structure analysis; this bifurcated bond is also supported by the observation based on the IR spectrum of the crystals.     

Synthetic studies on β-lactam antibiotics. VII. Mild removal of the benzyl ester protecting group with aluminum trichloride

The benzyl ester protecting group in β-lactam derivatives can be cleanly removed by treatment with aluminum trichloride under mild conditions, preferably in the presence of anisole, to give the corresponding free acids in high yields.     

DMPM (3,4-dimethoxybenzyl) protecting group for hydroxy function more readily removable than MPM (P-methoxybenzyl) protecting group by DDQ oxidation

The DMPM (3,4-dimethoxybenzyl) protection for hydroxy function was deprotected more readily than the MPM (p-methoxybenzyl) protection by DDQ oxidation under neutral conditions, and applied to the synthesis of some synthons to macrolide and polyether antibiotics.