Manganese(III)-based oxidation of 2,4-piperidinediones in the presence of alkenes

The manganese(III)-catalyzed aerobic oxidation of 2,4-piperidinediones was performed in the presence of alkenes at room temperature, producing 1-hydroxy-8-aza-2,3-dioxabicyclo[4.4.0]decan-7-ones in excellent yields. On the other hand, the 6-acetoxy-3-aza-7-oxabicyclo[4.3.0]nonan-2-ones were obtained by the oxidation of the 2,4-piperidinedione-3-carboxylates with manganese(III) acetate in the presence of alkenes at elevated temperature under an argon atmosphere. A similar oxidation using decarboxylated 2,4-piperidinediones produced the 2,3,6,7-tetrahydrofuro[3,2-c]pyridin-4(5H)-ones and/or 2,3,6,7-tetrahydrofuro[2,3-b]pyridin-4(5H)-ones in good yields. The structure determination and the decomposition reaction of the azabicyclic peroxides in acetic acid or acetic anhydride, and the reaction pathway were also described.     

New synthetic method to 1,2-benzisothiazoline-3-one- 1,1-dioxides and 1,2-benzisothiazoline-3-one-1-oxides from N-alkyl(o-methyl) arenesulfonamides

Various N-alkylsaccharins were easily prepared in moderate to good yields by the reaction of N-alkyl(o-methyl)arenesulfonamides with (diacetoxyiodo)benzene in the presence of iodine under irradiation with a tungsten lamp (W-hν). On the other hand, irradiation of N-alkyl(o- methyl)arenesulfonamide derivatives bearing various subslituents on the aromatic ring with a high- pressure mercury lamp (Hg-hν), in the presence of (diacetoxyiodo)benzene and iodine gave the corresponding N-alkyl-1,2-benzisothiazoline-3-one-1-oxide derivatives in moderate yields, together with N-alkyl-1,2-benzisothiazoline-3-one-1,1-dioxide (saccharin) derivatives.     

Crystal structure of hexagonal SrAl2O4 at 1073 K

The crystal structure of SrAl₂O₄ at 1073 K was determined from conventional X-ray powder diffraction data using direct methods, and it was further refined by the Rietveld method. The structure was hexagonal (space group P6₃, Z=6) with a=0.89260(3) nm, c=0.84985(2) nm and V=0.58639(3) nm³. Final reliability indices were R_wp=7.87%, R_p=5.87% and R_B=4.19%. The [AlO₄] tetrahedra are linked to form trigonally distorted rings and they are joined in layers. These layers are stacked with a two-layer repeat and connected by the tetrahedral apices. All of the Sr atoms occupy the centers of the rings when viewed along the c-axis. The structure is described as a stuffed derivative of tridymite.     

Simultaneous determination of calcium and magnesium by using a flow-injection system with simultaneous injection of two sample plugs and a masking agent plug

A flow-injection system is described for the simultaneous determination of calcium and magnesium with simultaneous injection of two sample plugs and a masking agent plug and with a single detector. The system utilizes the simultaneous injection of an ethylene glycol-bis(2-aminoethylether)-N,N,N',N'-tetra-acetic acid plug and two small sample plugs into the same carrier stream and which are merged downstream with 3,3'-bis[N,N-bis(carboxymethyl)aminomethyl)]-o-cresolphthalein solution for spectrophotometric determination of calcium and magnesium. The results for the analysis of natural waters by the proposed method correspond well with those obtained by the conventional titration method with ethylenediaminetetra-acetic acid, and showed good reproducibility. The rate of analysis is about 15 samples/hr.     

Thick Silicate Film by an Interfacial Polymerization

A thick silica gel film, corresponding to the glass film of 10–20 micron in thickness, has been formed at the interface between two immiscible liquids, hexane and water, using E-40, a partially polymerized silicon alkoxide, as the precursor. The film formation was possible using both acid- and base-catalyzed water, but was greatly dependent on the type of catalyst. Only the trace of a film was observed for the system catalyzed with a strong electrolyte such as HCl, HNO₃ or NaOH, while a gel film, corresponding to the glass film of several to 10 micron in thickness was formed with a weak electrolyte such as ammonia, organic acid like acetic acid, citric acid, etc., of similar pH value. The direct introduction of organic base catalyst like triethylamine in hexane was much more effective than the use of ammonia water, suggesting that the polymerization of E-40 to form a gel film takes place in the organic phase, where water molecules, as well as undissociated ammonia or organic acids, can diffuse in.