NAD(P)+–NAD(P)H models. 84. Stereochemistry controlled by the electronic effect from a sulfinyl group

2,3-Dihydro-2,2,4-trimethylthieno[3,2-b]pyridinium 1-oxide iodide ( 1 ) has been reacted with various inorganic and organic hydride donors. It has been found that the stereochemistry of reaction is controlled by the orientation of the sulfinyl dipole, and the relative bulkiness of substituents plays no role in determining the reaction face: a reactive hydride donor prefers to attack at the anti-face with respect to the sulfinyl dipole, whereas a less reactive hydride donor prefers to attack at the syn-face.     

Control of photochemistry of stilbazolium ion by adsorption to poly(potassium vinylsulfate) and to hectorite clay

Adsorption or intercalation of trans-1-methyl-4-(2-phenylvinyl)pyridinium ion (stilbazolium ion, SB ( 1 )) to a polyelectrolyte, i. e., poly(potassium vinylsulfate) (PVSK), and to a hectorite clay is studied and its effect on the photochemistry of SB examined. trans-cis Photoisomerization of SB molecularly adsorbed to PVSK proceeds efficiently as with free SB in water, while that of SB molecularly intercalated in the clay is markedly suppressed. Photodimerization proceeds efficiently with SB intercalated in the clay in the aggregated form. Overall photodecoloration, however, proceeds more efficiently with SB adsorbed to PVSK under multiple adsorption conditions apparently due to the higher mobility of PVSK-adsorbed SB compared to that of clay-intercalated SB.     

Solubility characteristics of C60 fullerenes with two well‐defined polystyrene arms in a polystyrene matrix

Four samples of C₆₀‐(PS)₂, i. e., C₆₀ fullerenes with two low‐polydispersity PS arms at the 1,4‐positions, were studied with respect to their solubility and dispersion state in a PS (polystyrene) matrix by the UV spectroscopic method. C₆₀‐bearing polymers were found to be dispersed, in a blend film or a bulk film of itself, either monomolecularly or in aggregates, depending on the chain length of the polymer moiety and blend composition.     

Stereochemistry in the reaction of alkylsulfinyl phenylmethyl carbanion with electrophiles

Stereochemistry of the reactions of methyl-, ethyl-, 2-propyl-, and 1,1-dimethylethylsulfinyl phenylmethyl carbanions with deuterium oxide and methyl iodide in tetrahydrofuran have been studied. The 2-propylsulfinyl phenylmethyl carbanion exerts abnormal behavior in the sense that the alkyl substituent herein has no ability to freeze the conformation of the carbanion. The results are interpreted in terms of hard and soft interactions. ⁷Li and ¹⁷O nuclear magnetic resonance (NMR) spectroscopy revealed that the carbanions derived from these sulfoxides behave as the oxylate form.