A simplified green chemistry approach to the Biginelli reaction using ‘Grindstone Chemistry’

Grindstone Chemistry--a greatly evolved version of Toda’s method of grinding solids together for solvent-free chemical reactions--has been described and its usefulness illustrated by the successful application of this technique to a simplified process for conducting the multi-component Biginelli reaction for the synthesis of physiologically active tetrahydropyrimidinones.     

Selective synthesis of dehydroamino acids from threonines

Dehydropeptides containing dehydroamino acid (ΔAA) are frequently found in natural resources with important biological activity. Herein, we report the selective synthesis of Z- and E-ΔAbu from l- and l-allo-threonine as starting materials through selenation and oxidative elimination. The detailed reaction mechanism of phosphine-assisted selenoether formation is also discussed.     

Microwave-accelerated Claisen rearrangements of allyl tetronates and tetramates

[3,3]-Sigmatropic rearrangements of allyl tetronates and allyl tetramates to give 3-allyltetronic or -tetramic acids, respectively, proceed within 20-60 min under microwave irradiation (300 W, 130-190 °C). Consecutive (homo)sigmatropic [1,5] H-shifts such as oxa-ene reactions are promoted less effectively, which allows the isolation of Claisen intermediates of sigmatropic domino sequences, in contrast to conventional heating.     

Stereological simulations of asymmetric polymerization in channels of bile acid inclusion compounds: A detailed analysis of the monomer arrangements in the channels

We studied simulations by computer graphics to estimate the steric mechanism of the asymmetric polymerization of prochiral diene monomers in channels of inclusion compounds of steroidal bile acids, such as deoxycholic acid (DCA) and cholic acid. We applied a hierarchization method to interpret the crystal structures of bile acids, clarifying that the chiral host molecules associated to form characteristic 2₁-helical assemblies with uneven surfaces. A detailed analysis of the uneven channels in a close-packing state indicated that there were many possible arrangements of the monomers in the channels. The plausible arrangements in the channel could explain a previous study, which showed that the polymerization in the DCA channel yielded chiral polymers with a predominant configuration from prochiral diene monomers, such as 2-methyl-trans-1,3-pentadiene. On the basis of such simulation studies of the arrangements of guest monomers in the channel, we examined a plausible steric mechanism for asymmetric inclusion polymerization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4648–4655, 2004     

Shear banding in strained semicrystalline polyamide 6 films as revealed by atomic force microscopy: Role of the amorphous phase

Atomic force microscopy (AFM) has been used to visualize the plastic deformation mechanisms that are responsible for the yielding of semicrystalline polymers of low degree of crystallinity (<50%). Indeed, AFM, if operated in suitable conditions, is able to image both the amorphous and the crystalline phases. Polyamide 6 films have been drawn at temperatures T < 160 °C. Postmortem AFM observations show that, at yield, shear bands nucleate and propagate in the amorphous phase. They cross the crystalline lamellae and run over the whole surface of the sample. By crossing the lamellae, they form nanoblocks of uniform size. Neither the size of the nanoblocks nor the angle between the tensile axis and the shear bands can be explained in terms of crystal plasticity. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 687–701, 2004     

Mutual influence of the morphology and capillary rheological properties in nylon/glass‐fiber/liquid‐crystalline‐polymer blends

Nylon‐6/glass‐fiber (GF)/liquid‐crystalline‐polymer (LCP) ternary blends with different viscosity ratios were prepared with three kinds of nylon‐6 with different viscosities as matrices. The rheological behaviors of these blends were characterized with capillary rheometry. The morphology was observed with scanning electron microscopy and polarizing optical microscopy. This study showed that although LCP did not fibrillate in binary nylon‐6/LCP blends, LCP fibrillated to a large aspect ratio in some ternary blends after GF was added. The addition of 5 wt % LCP significantly reduced the melt viscosity of nylon‐6/GF blends to such an extent that some nylon‐6/GF/LCP blends had quite low viscosities, not only lower than those of neat resins and nylon‐6/GF blends but also lower than those of corresponding nylon‐6/LCP blends. The mutual influence of the morphology and rheological properties was examined. The great reduction of the melt viscosity was considered the result of LCP fibrillation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1619–1627, 2004     

Pressure and temperature dependence of the gas‐transport properties of dense poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] membranes

The gas‐transport properties of poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] (6FDA‐2,6‐DAT) have been investigated. The sorption behavior of dense 6FDA‐2,6‐DAT membranes is well described by the dual‐mode sorption model and has certain relationships with the critical temperatures of the penetrants. The solubility coefficient decreases with an increase in either the pressure or temperature. The temperature dependence of the diffusivity coefficient increases with an increase in the penetrant size, as the order of the activation energy for the diffusion jump is CH₄ > N₂ > O₂ > CO₂. Also, the average diffusion coefficient increases with increasing pressure for all the gases tested. As a combined contribution from sorption and diffusion, permeability decreases with increases in the pressure and the kinetic diameter of the penetrant molecules. Even up to 32.7 atm, no plasticization phenomenon can be observed on flat dense 6FDA‐2,6‐DAT membranes from their permeability–pressure curves. However, just as for other gases, the absolute value of the heat of sorption of CO₂ decreases with increasing pressure at a low‐pressure range, but the trend changes when the feed pressure is greater than 10 atm. This implies that CO₂‐induced plasticization may occur and reduce the positive enthalpy required to create a site into which a penetrant can be sorbed. Therefore, a better diagnosis of the inherent threshold pressure for the plasticization of a glassy polymer membrane may involve examining the absolute value of the heat of sorption as a function of pressure and identifying the turning point at which the gradient of the absolute value of the heat of sorption against pressure turns from a negative value to a positive one. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 354–364, 2004