Regioselective allylzincation of alkenylboronate

[reaction: see text] Boryl substitution on an olefin activates the olefinic double bond toward addition of an organozinc reagent. Addition of an allylic zinc reagent to an alkenylboronate thus takes place smoothly to afford a variety of gem-zincio/boryl species. Theoretical studies with density functional calculations on the reaction pathway revealed that the reaction proceeds via a zincio-ene reaction rather than a bora-Claisen rearrangement.     

Structural change of water by gelation of curdlan suspension

Phase transition of water restrained by curdlan suspension annealed at a temperature from 20 to 110°C was investigated by differential scanning calorimetry (DSC). The melting temperature of water restrained by annealed curdlan discontinuously decreased at around 60°C, while the amount of bound water calculated from enthalpy of melting increased at 60°C, regardless of water content. Using a highly sensitive DSC, curdlan suspension with various concentrations was studied. It was found that an endothermic transition was observed at ca. 58°C in a wide range of concentrations. The transition observed at 60°C is thermo-reversible and both temperature and transition enthalpy are constant even after gel formation. Well equilibrated suspension at a temperature lower than 60°C formed no gel.     

Melting behavior of nylon 6 fiber in textiles

The melting process of constrained nylon 6 fibers has been studied to estimate the true melting point of its original crystals. The melting peak became simpler in shape and shifted to higher temperature with increasing fiber-axis restricting force. When heating rate, β, was increased, the temperature where the melting curve initially departs from its baseline, Tsm, decreased steeply in the range of 45 to 60°C min^-1, and increased linearly with increasing β above 60°C min^-1. By linear extrapolation of Tsm to 0°C min^-1, the temperature of ca 190°C was obtained for the melting temperature of the original nylon 6 crystals. This seems to correspond to the zero-entropy-production melting of the most imperfect crystallites of the nylon 6 fabric. This revised version was published online in July 2006 with corrections to the Cover Date.     

Measurements of equilibrium water vapor pressures for the dehydration of magnesium, manganese and cobalt formate dihydrates by means of the transpiration method

The equilibrium water vapor pressures for the thermal dehydration of Mg(HCO(2))(2). 2H(2)O, Mn(HCO(2))(2). 2H(2)O and Co(HCO(2))(2). 2H(2)O were measured by means of the transpiration method. These hydrates form isomorphous crystals with space group P21/c. In this structure, the water molecules lie in the planes parallel to the (100) planes. Thermodynamic data such as DeltaG, DeltaH and DeltaS were derived from the values of the water vapor pressures. The relationship between these thermodynamic data and the crystal structures is discussed.     

Biodegradable Polyurethanes from Plant Components

Abstract

Polyurethane (PU) sheets and foams having plant components in their network were prepared by using the following procedure. Polyethylene glycol (PEG) was mixed with one of the following; molasses, lignin, woodmeal, or coffee grounds. The mixture obtained was reacted with diphenylmethane diisocyanate (MDI) at room temperature, and precured PUs were prepared. The precured PUs were heat-pressed and PU sheets were obtained. In order to make PU foam, the above mixture was reacted with MDI after the addition of plasticizer, surfactant (silicone oil), catalyst (di-n-butyltin dilaurate), and droplets of water under vigorous stirring. The glass transition temperature, tensile and compression strengths, and Young's modulus of the PU sheets and foams increased with an increasing amount of plant components. This suggests that saccharide and lignin residues act as hard segments in PUs. It was found that the PUs obtained were biodegradable in soil. The rate of biodegradation of the PUs derived from molasses and coffee grounds was between that of cryptomeria (Cryptomeria japonica) and beech (Fagus sieboldi).     

Synthetic Studies on Spirolides A and B: Formation of the Upper Carbon Framework Based on a Lewis Acid Template-Catalyzed Diels–Alder Reaction

The upper fragment of spirolides A and B, which are marine phycotoxins that exhibit strong antagonistic activities on nicotinic acetylcholine receptors, was constructed. The functionalized cyclohexene in spirolides was stereoselectively synthesized from the bicyclic lactone, which could be readily accessed by the Lewis acid template-catalyzed asymmetric Diels–Alder reaction of the pentadienol and methyl acrylate.     

Total Synthesis of Lajollamycin B

The first total synthesis of lajollamycin B, a structurally novel nitro-tetraene spiro-β-lactone/γ-lactone antibiotic, is described. The convergent synthesis involves the construction of the C8′–C11′ nitrodienylstannane and its coupling with the segment prepared from the C1′–C7′ ω-iodoheptadienoic acid and the right-hand heterocyclic fragment, which has been utilized for our previous syntheses of oxazolomycin A. The revision of the geometry of the terminal Δ^{10′, 11′}-double bond from E to Z is also described for the structure of natural lajollamycin B.