Cyanide-Free One-Pot Synthesis of Methacrylic Esters from Acetone

Methacrylic esters, represented by methyl methacrylate (MMA), are widely used as commodity chemicals. Here, the one-pot synthesis of methacrylic esters from acetone, a haloform and alcohols in the presence of an organic base is described. Using DBU as the organic base for the reaction of acetone, chloroform and methanol in acetonitrile afforded MMA in 66 % yield. When the solvent was replaced by benzonitrile, the product MMA was successfully purified by distillation. Applicability of this process to various alcohols was also investigated to show ethyl, phenyl, CF₃CH₂, and n-C₆F₁₃CH₂CH₂ esters were obtained in moderate yields. The use of bromoform instead of chloroform resulted in the improvement of the yield, for example, methyl and n-C₆F₁₃CH₂CH₂ esters up to 81 and 70 %, respectively. The reaction with deuterated starting materials acetone-d₆ and MeOH-d₄, with DBU in acetonitrile afforded deuterated MMA (MMA-d₈) in 70 % yield.     

A simple and sensitive method for the determination of hydroxylamine in fresh-water samples using hypochlorite followed by gas chromatography.

A new and simple method for the determination of hydroxylamine in environmental water, such as fresh rivers and lakes using hypochlorite, followed by its gas choromatographic detection, has been developed. A glass vial filled with sample water was sealed by a butyl-rubber stopper and aluminum cap without head-space, and then sodium hypochlorite solution was injected into the vial through a syringe to convert hydroxylamine to nitrous oxide. The head-space in the glass vial was prepared with 99.9% grade N2 using a gas-tight syringe. After the glass vial was shaken for a few minutes, nitrous oxide in the gas-phase was measured by a gas chromatograph with an electron-capture detector. The dissolved nitrous oxide in the liquid-phase was calculated according to the solubility formula. The proposed method was applied to the analysis of fresh-water samples taken from Iu river and Hii river, flowing into brackish Lakes Nakaumi and Shinji, respectively.     

Malyngamide X: The First (7R)‐Lyngbic Acid that Connects to a New Tripeptide Backbone from the Thai Sea Hare Bursatella leachii

Malyngamide X ( 1 ), the first (7R)‐lyngbic acid connected to a new tripeptide backbone, was isolated from the Thai sea hare Bursatella leachii. The gross structure of 1 was established on the basis of 1D and 2D NMR and mass spectroscopic data. Combination of the NMR spectroscopic experiments with α‐methoxy‐α‐(trifluoromethyl)phenylacetic acid esters, 2,2,2‐trifluoro‐1‐(9‐anthryl)ethanol chiral solvating agent, and molecular mechanics of 1 and the synthetic molecular fragments allowed us to determine the absolute stereochemistry of all six stereogenic centers without hydrolytic degradation of the compound. Compound 1 displayed moderate cytotoxic, antitubercular, and antimalarial properties.     

Martin Boundaries of Elliptic Skew Products, Semismall Perturbations, and Fundamental Solutions of Parabolic Equations

We consider positive solutions of elliptic partial differential equations on non-compact domains of Riemannian manifolds. We explicitly determine Martin boundaries and Martin kernels for a class of elliptic equations in skew product form by exploiting and developing perturbation theory for elliptic equations and short/long-time estimates for fundamental solutions of parabolic equations.     

Iodine catalyzes C-glycosidation of d-glucal with silylacetylene

A convenient method for C-glycosidation (alkynylation) with various silylacetylenes to d-glucal by iodine molecule via iodo-oxonium intermediates provided exclusively the α-acetylene glycoside products. Eleven successful examples are shown under this condition.     

The synthesis and reaction of N-sulfenyl heterocycles: development of effective sulfenylating reagents

Various N-sulfenyl heterocycles were synthesized by transamination of sulfenamides using a chlorine gas-free method. The N-sulfenyl heterocycles behaved as sulfenylating reagents of anilines; N-sulfenylbenzimidazoles were the most effective.     

Preparation and characterization of mesoporous silica thin films from polyethoxysiloxanes

Tetraethoxysilane (TEOS) and polyethoxysiloxanes (PEOSs; prepared by the acid‐catalyzed hydrolytic polycondensation of TEOS) were subjected to the sol–gel process in the presence of cetyltrimethylammonium bromide (CTAB), respectively. The PEOSs with M_w 700–26,000, as prepared by sol–gel coating of TEOS and PEOS under various conditions, were used. Uniform and crack‐free thin films of thickness 276–613 nm were prepared by spin‐coating of a PEOS solution containing CTAB. When the coating films were sintered at 400 °C, the combustion of ethoxy groups and CTAB took place to provide porous silica thin films. The structure of the thin films was found to be dependent on the molecular weight of PEOS and the molar ratio of CTAB/Si: lamellar or hexagonal phase was observed for M_w less than 15,000 and for CTAB/Si molar ratios greater than 0.10. Honeycomb structures were observed for M_w less than 5000 and for CTAB/Si molar ratios of 0.15. The honeycomb structure was also observed by atomic force microscopy and transmission electron microscope. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2542–2550, 2006