The first total synthesis of (+)-(Z)-laureatin

The stereoselective total synthesis of (+)-(Z)-laureatin is described. The 3,8-dioxabicyclo[5.1.1]nonane skeleton possessing trans-orientated alkyl substituents at the α,α′-positions to the ether linkage was stereoselectively constructed via formation of the oxetane arising from 4-exo cyclization of hydroxy epoxide existing on the oxocene core.     

Electrical and magnetic properties of ion-exchangeable layered ruthenates

An ion-exchangeable ruthenate with a layered structure, K_0.2RuO_2.1, was prepared by solid-state reactions. The interlayer cation was exchanged with H⁺, C₂H₅NH₃⁺, and ((C₄H₉)₄N⁺) through proton-exchange, ion-exchange, and guest-exchange reactions. The electrical and magnetic properties of the products were characterized by DC resistivity and susceptibility measurements. Layered K_0.2RuO_2.1 exhibited metallic conduction between 300 and 13 K. The products exhibited similar magnetic behavior despite the differences in the type of interlayer cation, suggesting that the ruthenate sheet in the protonated form and the intercalation compounds possesses metallic nature.     

Design and preparation of pulsatile release tablet as a new oral drug delivery system.

To achieve time-controlled or site specific delivery of a drug in the gastrointestinal tract, an orally applicable pulsatile drug release system with the dry-coated tablet form was developed. The system consisted of a less water permeable outer shell and a swellable core tablet; from such a system, the drug was expected to be rapidly released after a certain period of time on the basis of time-controlled disintegration mechanism. Various model disks of outer shell, consisting of hydrogenated castor oil and polyethyleneglycol 6000, were tested for their water penetration rate. The experimental results showed that water penetration proceeded obeying the boundary retreating mechanism, so that the lag time of the system could be controlled by changing either the thickness or the composition of the outer shell. The swelling force of various commercially available disintegrants was quantitatively compared, and it was found that carboxymethylcellulose calcium was the preferable disintegrant to be used for the core tablet. On the basis of the results of a series of fundamental studies, various pulsatile release tablets of isoniazide with different lag times were designed. In the in vitro dissolution test, typical pulsatile release was achieved for all the tablets prepared, and a good correlation was found between the observed lag time and the estimated lag time calculated from an empirical equation deduced from the thickness and polyethyleneglycol 6000 content of the outer shell.     

Crystal chemistry and thermodynamic properties of anisotropic Ce2Ni7H4.7 hydride

A new intermetallic deuteride Ce₂Ni₇D_4.7 with an anomalous volume expansion has been studied. Its structure was solved on the basis of in situ neutron diffraction data. Expansion proceeds along the c-axis and within the CeNi₂ slabs only. All D atoms are located inside these slabs and on the border between CeNi₂ and CeNi₅. Ordering of D atoms in the bulk of CeNi₂ is accompanied by substantial deformation of these slabs thus lowering the hexagonal symmetry to orthorhombic [space group Pmcn (No. 62); a=4.9251(3) Å, b=8.4933(4) Å, c=29.773(1) Å]. Inside the CeNi₂ layer the hydrogen sublattice is completely ordered; all D-D distances exceed 2.0 Å. Local coordination of Ni by D inside the CeNi₂ blocks is of “open”, saddle-like type. Hydrogen ordering is mainly determined by Ce-H and H-H interactions. The pressure-composition-temperature measurements yielded the following thermodynamic parameters of the formation of the hydride: ΔH=−22.4 kJ/mol_H, ΔS=−59.9 J/(K mol_H).     

13C- and 1H-NMR and FTIR spectroscopic evidence for aggregate formation of organosilanes in toluene

 Changes in the ¹³C and ¹H NMR chemical shifts of the silane coupling agent (3-aminopropyltri-ethoxysilane, APTS) in toluene, which were detected as the concentration of APTS increased, have been interpreted in terms of the formation of micelles and the presence of a critical micelle concentration (CMC) equal to ca. 0.47 mol 1^-1. For the protons of the n-propyl segment, ¹H NMR splitting patterns have been analyzed and conformations of the propyl segment have been discussed. Plots of relative absorbance of the two NH₂ stretch IR bands at 3324 and 3384 cm^-1 against concentration provided an inflection point (corresponding to the CMC) at a value equal to 0.46 mol 1^-1. Thus, consideration of the interaction of APTS with a surface must take into account the presence of both APTS aggregates as well as APTS monomers. Received: 16 August 1996 Accepted: 26 September 1996     

Surfactants having polyfluoroalkyl chains. II. Syntheses of anionic surfactants having two polyfluoroalkyl chains including a trifluoromethyl group at each tail and their flocculation-redispersion ability for dispersed magnetite particles in water

Anionic surfactants having two polyfluoroalkyl chains per molecule, i.e. the sodium salt of bis(1H, 1H, 2H,2H-heptadeca-fluorodecyl)-2-sulfosuccinate, CF₃(CF₂)₇(CH₂)₂OCOCH₂CH(SO₃Na)COO(CH₂)₂(CF₂)₇CF₃, the sodium salt of bis(1H, 1H, 2H, 2H-tridecafluoro-octyl)-2-sulfosuccinate, CF₃(CF₂)₅(CH₂)₂OCOCH₂CH(SO₃Na)COO(CH₂)₂(CF₂)₅CF₃, and the sodium salt of bis(1H, 1H, 2H, 2H-nonafluorohexyl)-2-sulfosuccinate, CF₃(CF₂)₃(CH₂)₂OCOCH₂CH(SO₃Na)COO(CH₂)₂(CF₂)₃CF₃, have been prepared from maleic anhydride, the corresponding alcohols possessing a polyfluoroalkyl chain and sodium hydrogen sulfite. The flocculation and redispersion abilities of these surfactants for dispersed magnetic particles in water have been examined to investigate the effect of the chain length. It was found that this ability was enhanced by an increase in the chain length. The contact angles for water for pelleted surface-modified magnetite have been measured. In order to compare this ability and the contact angles, data for other fluorinated surfactant have been obtained. The Kraff point, the surface tension and the pNa of the aqueous surfactant solutions have also been measured.     

Alkyl Derivatives of Boehmite Having the Second Stage Structure

Abstract

The reaction of aluminum alkoxide in straight-chain primary alcohols at elevated temperatures yielded the alkyl derivatives of boehmite [AlO(OH)_1-x (OR) _x ], a class of intercalation compound where the guest moieties are covalently bonded to the host boehmite layers. The addition of small amounts of water to the reaction system yielded another phase having a larger basal spacing. XRD, IR, and elemental analysis showed that the products had the boehmite layer structure with the alkyl moieties incorporated between the boehmite layers. IR spectra of the products also exhibited bands due to hydrogen bonding between the boehmite layers. These results suggest that the products are the alkyl derivatives of boehmite having the second stage structure. Because water in the reaction medium facilitated the hydrolysis of intermediate aluminum alkoxides, the product with the second stage structure had smaller alkyl/Al ratio and therefore had smaller basal spacing than that expected from the corresponding first stage product.     

Synthesis and properties of optically active 1,3-diols and their derivatives as chiral dopants for ferroelectric liquid crystals

Abstract

New chiral dopants β-hydroxy ketones 1, 1,3-diols 2, 1,3-dioxanes 3 and 1,3-dioxan-2-ones 4 were designed and synthesized. Reaction of (R)-1,2-epoxyoctane with carbanions derived from 2-(4-substituted phenyl)-1,3-dithianes followed by hydrolysis of the resulting hydroxy dithianes afforded 1. Reduction of 1 gave the diols 2, which yielded 3 upon acetalization and 4 upon carbonation. The syn isomers of 2, 3, and 4 exhibited larger spontaneous polarizations, when applied as chiral dopants, than the anti isomers or hydroxy ketones 1.