Synthesis of Unsymmetrical Ketones Using Chelation-Controlled Sequential Substitution of -Triazinylamide/Weinreb Amide by Organometallic Reagents.

-(2,4-Dimethoxy-1,3,5-triazinyl)amide was found to exhibit similar behavior to -methoxy--methylamide (Weinreb amide) but higher reactivity for nucleophilic substitution by organometallic reagents. Triazinylamide suppresses overaddition, leading to the formation of a tertiary alcohol by the chelating ability of the triazinyl and carbonyl groups. Ureas possessing both triazinylamino and methoxy(methyl)amino groups underwent sequential nucleophilic substitution with different organometallic reagents, which furnished unsymmetrical ketones without any detectable tertiary alcohols.

Dynamic solvent effects in radical-radical coupling reactions: an almost bottleable localised singlet diradical.

Localised singlet diradicals are key intermediates in bond homolysis, which plays a crucial role in chemical reactions. However, thorough experimental analyses of the reaction dynamics and chemical properties are generally difficult because bond formation is rapid, even under low-temperature matrix conditions. In this study, the effects of solvent and pressure on the lifetimes of long-lived singlet diradicals with bulky substituents were investigated.

Long-Time Relaxation of Stress-Induced Birefringence of Microcrystalline Alkali Halide Crystals.

Alkali halide single crystals are most commonly used as the diluent matrix in the tablet method or disk technique for spectroscopic measurements. However, stress-induced birefringence (SIB) of alkali halides as well as intrinsic birefringence manifest during the disk formation process. Thus, the true chiroptical measurement is disturbed by optical anisotropies (OA) containing SIB and intrinsic birefringence, except in the case of optical homogeneity.

Dynamic solvent effects on the thermal isomerization of zinc dithizonate.

The pressure dependence of the rate constant for the thermal isomerization of zinc dithizonate was measured at various temperatures in highly viscous solvents, i.e., glycerol triacetate and 2,4-dicyclohexyl-2-methylpentane, as well as in their chemically similar nonviscous solvents, such as methyl acetate and methylcyclohexane.