X-Ray crystallography of ethylpalladium thiolato complex, trans-PdEt(SPh)(PMe3)2, shows the detailed features of the Pd–C and Pd–S bonding. Reaction of the complex with CO at 5 atm gives S-phenyl thiopropionate. The NMR spectrum of the reaction mixture under 1 atm of CO shows the presence of trans-Pd(COEt)(SPh)(PMe3)2 formed through CO insertion into the Pd–C bond.
The association behavior of protoporphyrin IX was investigated at different pH by absorption spectroscopy and gel chromatography. Protoporphyrin IX existed as monomer in acidic water, as aggregate in neutral water, and as dimer in basic water. Poly(N-vinylpyrrolidone) tended to suppress dimerization and aggregation of protopophyrin IX.
Various 2,2,2-trifluoroethyl onium triflates were synthesized by treating tertiary amines, pyridines, quinoline, a triazole, sulfides, and a phosphine with (2,2,2-trifluoroethyl)phenyliodonium triflate. Sulfoxides and N-oxide were converted to the corresponding trifluoroethylated salts. As an application, CsF-treatment of (2,2,2-trifluoethyl)triphenylphosphonium triflate with an aldehyde was shown to produce a trifluoromethylated olefin.
Methyl propargyl ethers, obtained from carbonyl compounds by successive treatment with an acetylide and MeI, were easily converted to the corresponding α,β-unsaturated ketone by regioselective hydration of acetylenic moiety followed by elimination of methanol under the catalytic action of Au(III).
Capture of unstable carbon oxides formed by the reduction of carbon dioxide (CO2) with benzoin carbanion using phenyliodonium bis(phenylsulfonyl)methylide (1) was tried. In this reaction decomposition of the ylide 1 by the unstable carbon oxides was observed to give phenylsulfonylcarbene : CH(SO2Ph).
2-(Octadecyldithio)pyridine (1) and 5-(octadecyldithio)-2-nitrobenzoic acid (2) were synthesized in order to prepare Langmuir–Blodgett (LB) membranes which possess reactive dithio groups on the surface for further modification with enzymes. The monolayer membrane, composed of 1 or 2, was deposited successfully on an ion-sensitive field effect transistor, and the membrane surface was modified with urease covalently by a thiol–disulfide exchange reaction. The LB membrane-based sensor 2 showed a better potentiometric response to urea than that of the membrane-based sensor 1. The results are discussed on the basis of the reactivity of the dithio groups to urease at the membrane surface.
The compounds Ag7TaS6 and Ag7NbS6 were prepared by a sealed silica tube method at 500°C for 4 d. They crystallize in the face-centered cubic system with the unit-cell dimensions of a=10.5139±0.0003 Å and a=10.5001±0.0006 Å, respectively. From the density measurements, it has been clarified that the unit cell contains four formula units.
The partition coefficients of 21H,23H-porphine (H2por) and its copper(II) (Cu(por)) and zinc(II) (Zn(por)) complexes were determined in nonaqueous two-phase systems. A linear free-energy relationship was observed between the partition coefficients of H2por and Cu(por). The partition coefficient of Zn(por) was suppressed by coordination bonding with the polar solvent molecules.
The complex formation reaction between crown ethers and bivalent transition metal ions was investigated. Although the obtained equilibrium constants were generally small, there was a case where the constant was larger than that for the crown ether–alkali metal system. From kinetic studies the reactions were found to obey the Eigen’s mechanism.
Dielectric relaxation studies of dialkyl ethers of ethylene glycol and of diethylene glycol have been carried out at microwave frequencies in benzene solutions. Dipole moment and relaxation times corresponding to overall and group rotations and their weight factors have been determined. The configuration of these molecules and the mechanism of the rotation of end alkoxyl groups have been discussed.
3-(p-Ethoxybenzoyl)acrylic acid (1) reacts with 3-methyl-1-phenyl-2-pyrazolin-5-one to give an addition compound 2. The condensation of 2 with hydrazine hydrate affords 4,5-dihydro-3(2H)-pyridazinone (3a). Reaction of 3a with dimethyl sulfate, diethyl sulfate, ethyl bromoacetate, POCl3, and P2S5 gave the N-substituted pyridazinones 3b–d, a dichloro derivative 5a, and a dithione 7. The behavior of the dichloro and the dithione derivatives was studied toward different reagents. The in vitro antibacterial screening reveals moderate activity against Gram-positive for compounds 3a and 3c while 4 and 7 are inactive.
It has been established that phosphorus containing alkylammonium salts obtained by alkylation of primary amines with bis(2-chloroethyl) phosphonate or alkyl 2-chloroethyl phosphonate can be transformed into corresponding compounds with aziridine ring.