Structure and properties of the mesophase of syndiotactic polystyrene. II. Effect of stepwise extraction on the preparation of the mesophase

In this study, a novel stepwise extraction method has been examined. The guest molecules housed between the helices of the clathrate δ form of syndiotactic polystyrene can be removed completely with this method. A systematic study of the preparation of a solvent‐free mesophase (emptied clathrate) membrane, its helical and residual solvent contents, and its structural transformations has been performed. In this first attempt, an enhancement in the TTGG helical content has been observed in the extracted membrane, and a conceptual mechanism is proposed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 269–273, 2003     

Structure and properties of the mesophase of syndiotactic polystyrene—III. Selective sorption of the mesophase of syndiotactic polystyrene

Syndiotactic polystyrene (sPS) has various crystalline forms such as α, β, γ, and δ forms, and a mesophase depending on the preparation method. In this study, we focused on the mesophase with the molecular cavity of sPS, which is obtained by step‐wise extraction of the guest molecules from the sPS δ form. To prepare the mesophase containing different shapes and sizes of the cavity, two kinds of the sPS δ form membrane cast from either toluene or chloroform solution were first prepared and then the guest molecules were removed by a step‐wise extraction method using acetone and methanol. We could succeed in the preparation of two kinds of mesophase with different shapes and sizes of the molecular cavity. Either toluene or chloroform vapor sorption to the sPS mesophase membranes was examined at 25 °C. Sorption analysis indicates that the mesophase with large molecular cavities can mainly sorb large molecules; on the other hand, the mesophase with small cavities can sorb only the small molecules, and is unable to sorb a large amount of large molecule because the cavity was too small to sorb the large molecules. Therefore, the sPS mesophase membrane has sorption selectivity based on the size of the molecular cavity. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 238–245, 2004     

Field optimized initial state based control of photodissociation

A new scheme for controlling photodissociation through preparation of a variationally optimized linear superposition of field free vibrational eigenstates is applied for selective control of IBr and HI dissociation. The dependence of photodissociation on various field parameters and initial conditions is examined to investigate the mechanistic basis of selective control. The parametric equations of motion approach for determining vibrational dynamics as a function of field parameters without having to solve the time dependent Schrödinger equation explicitly for each field parameter separately is outlined and its use to identify field characteristics which will provide the requisite population mix represented by the optimal linear superposition of vibrational states is advocated.     

Microwave promoted methylation of plant polysaccharides

O-Methylation is of outstanding importance in structural polysaccharide chemistry. A novel method for the methylation of polysaccharides using microwave (MW) irradiation is described. Seed gum from Cyamopsis tetragonolobus (Guar) was fully methylated with dimethyl sulphate and sodium hydroxide using 100% microwave power for 4 min in 68% yield. The completely methylated seed gum thus obtained was hydrolyzed by 70% formic acid followed by 0.5N H₂SO₄ under full microwave power for 1.16 and 1.66 min, respectively. The partially methylated monosaccharides were separated and identified.     

Deoxygenation of sulfoxides, selenoxides, telluroxides, sulfones, selenones and tellurones with Mg-MeOH

The deoxygenation of a variety of sulfoxides, selenoxides, telluroxides, sulfones, selenones and tellurones has been reported with Mg-MeOH at room temperature in nearly quantitative yields. The deoxygenation is proposed to proceed by SET from Mg to the substrate.     

alpha-thiocyanation of carbonyl and beta-dicarbonyl compounds using (dichloroiodo)benzene-lead(II) thiocyanate

The combination reagent (dichloroiodo)benzene and lead(II) thiocyanate in dichloromethane effects oxidation of various enol silyl ethers, ketene silyl acetals, and beta-dicarbonyl compounds, thereby providing an efficient and convenient method for alpha-thiocyanation of carbonyl and beta-dicarbonyl compounds.     

Synthesis and binding studies of new bis-calix[4]arenes containing aromatic and heteroaromatic units

A series of new bis-calix[4]arenes containing different aromatic and heteroaromatic moieties have been synthesized. The complexing behavior of these bis-calix[4]arenes have been studied towards different metal ions and it has been found that these bis-calix[4]arenes bind silver ions selectively over other metal ions. The complexation has been studied by liquid-liquid extraction and by NMR and IR spectroscopy.     

Investigation of the reactions of fluorinated isatins and N-acetylisatins with thiocarbohydrazide: Synthesis of a novel spiro system: 2-oxo-1′,2′,4′,5′-tetrahydrospiro[3H-indole-3,3′-1,2,4,5-tetrazine]-6′-thione

A novel system 2-oxo-1′,2′,4′,5′-tetrahydrospiro[3H-indole-3,3′-1,2,4,5-tetrazine]-6′-thione has been synthesized by the treatment of fluorinated isatins with thiocarbohydrazide in aqueous ethanolic medium. Under exactly similar conditions, N-acetylisatin gave exclusively thiocarbohydrazone. The spiro product, on treatment with acetic acid, gave fluorinated isoindigo. Characterization of these products have been done by elemental analyses, ir, pmr and mass spectral studies.     

Stereoselective synthesis of all stereoisomers of vicinal and distal bis(O-2-aminoethyl)-p-tert-butylthiacalix[4]arene

O,O″- and O,O′-bis(2-aminoethyl)-p-tert-butylthiacalix[4]arenes of anti conformation have been prepared by the reduction of the corresponding O,O″- and O,O′-bis(cyanomethyl) ethers. Their syn-O,O″- and O,O′-counterparts have been prepared by alternative routes via the Mitsunobu reaction of thiacalix[4]arene with N-(2-hydroxyethyl)phthalimide and the reduction of a O,O′-disiloxanediyl-bridged O″,O?-bis(cyanomethyl) ether of 1,2-alternate conformation, respectively. These products are expected to serve as useful precursors of highly elaborated synthetic receptors, including biscalixarenes.     

Protic acid (HClO4 supported on silica gel)-mediated synthesis of 2,3-unsaturated-O-glucosides and a chiral furan diol from 2,3-glycals

Perchloric acid supported on silica gel acts as an excellent reagent system in converting glucals into 2,3-unsaturated-O-glucosides in good to excellent yields in short reaction time with good alpha selectivity. Primary, secondary, and allylic alcohols, phenols, and thiols react with 3,4,6-tri-O-acetyl glucal with equal ease. In addition to this, a chiral furan diol is obtained from unprotected D-glucal or D-galactal in good yields.