Chiral guest in a chiral framework: X-ray diffraction study

The inclusion compound of zinc lactate terephthalate with R-butan-2-ol, [Zn₂(R-Bu^sOH) (bdc)(S-lac)]?(R-Bu^sOH) (Bu^sOH is butan-2-ol, H₂bdc is terephthalic acid, S-H₂lac is lactic acid), was prepared by soaking crystals of [Zn₂(dmf)(bdc)(S-lac)]?DMF in pure R-butan-2-ol. The positions of chiral alcohol molecules in voids of the chiral framework and the host–guest contacts were determined by X-ray diffraction. These data provide an explanation for the origin of chiral discrimination of zinc lactate terephthalate toward the R-isomer of butan-2-ol.     

Synthesis of γ-butyrolactone fused cyclooctene

The expeditious route for the synthesis of γ-butyrolactone fused cyclooctene starting from the γ-butyrolactone fused cyclopentane through bicyclo[4.2.1]nonan-9-one is reported. Retro-Dieckmann’s condensation of bicyclo[4.2.1]nonan-9-one in presence of sodium methoxide and methanol furnished γ-butyrolactone fused cyclooctene in good yield. Surprisingly, the stereochemistry of ring-junction of γ-butyrolactone fused cyclooctene is different from the γ-butyrolactone fused cyclopentane, and the position of new ester group, which were confirmed unambiguously by X-ray analysis.     

Microwave-assisted asymmetric ring opening of meso-epoxides with aromatic amines catalyzed by a Ti-S-(−)-BINOL complex

Catalytic asymmetric ring opening of cyclohexene oxide and meso-stilbene oxide with anilines was catalyzed by a Ti-(S)-(−)-BINOL complex to afford β-amino alcohols in high yield (up to 95%) and good enantioselectivities (ee up to 55%) under microwave irradiation. The reaction using a microwave was found to be 10 times faster than traditional oil-bath heating with retention of enantioselectivity.     

Effects of Organic Salts on the Rate of Alkaline Hydrolysis of Phthalimide in the Presence Ofcationic Micelles

Pseudo-first order rate constants (k_obs) for alkaline hydrolysis of phthalimide (PTH), obtained at constant concentration of cetyltrimethylammonium bromide (CTABr) and 35°C, vary with the concentration of organic salts ([MX]) according to the relationship: k_obs = (k₀ + K [MX])/(1 + K [MX]) where and K are empirical parameters. The values of K at 0.01 M CTABr are nearly 2 times larger than the corresponding K values at 0.02 M CTABr for sodium benzoate, disodium phthalate and disodium isophthalate.     

Synthesis, characterization, and reactivity of new copper(II) complexes of 2-methylthio-N-(2-pyridylmethyl)acetamide

Copper(II) complexes were prepared with the new N(2)S(thioether) ligand 2-methylthio-N-(2-pyridylmethyl)acetamide (2-HL(N2S)). [Cu(2-L(N2S))Cl(MeOH)], which formed in the presence of excess triethylamine, is a distorted square pyramidal complex containing the ligand with the amide nitrogen deprotonated. The structurally analogous complex, [Cu(2-HL(N2S))Cl(2)], which formed in the absence of triethylamine, contains 2-HL(N2S) in the tautomeric imidic acid form. Neutral copper(II) N(2)S(thioether)S(thiolate) species were generated by addition of alkyl or aromatic thiolates to [Cu(2-L(N2S))Cl(MeOH)] and an unusual decomposition pathway was discovered.     

Studies with model membranes. IX. Evaluation of thermodynamic parameters from the transition state theory of rate processes for electrolyte diffusion through silver chloride parchment-supported membranes

Diffusion rate of biologically important electrolytes through parchment-supported silver chloride membrane have been determined by the use of Nernst-Planck equation at various temperatures taking into account membrane resistance R_m, membrane potential E_m, etc. The diffusion rates were found to be primarily dependent upon the difference in the hydration energies of the counterion in the external solution. On the basis of Eisenman-Sherry theory the diffusion rate sequence of alkali metal cations point towards the weak field strengths of the fixed charge groups. The various thermodynamic parameters, namely, ΔH^?, ΔF^?, and ΔS^? were evaluated. The values of ΔS^? found to be negative, indicating that the diffusion is taking place with partial immobilization in the membrane phase. A formal relation between ΔH_hydration, ΔF_hydration, and ΔS_hydration of cations with the corresponding values of ΔH^?, ΔF^?, and ΔS^? for diffusion was also found to exist for the investigated system.