Fatty alcohol ethers, nonionic surfactants which are used as general purpose emulsifiers were separated by use of water-modified carbon dioxide mobile phase in capillary supercritical fluid chromatography. Much greater peak intensities and improved separation were observed in the chromatogram with on-line modified mobile phase than with pure CO2. A simple method for the preparation of on-line modified mobile phase is also introduced.

Two different acyl substituents were introduced at the lower rim of calix[4]arene by the two step reactions. Calix[4]arenes (1) reacted with 3,5-dinitrobenzoyl chloride to yield monosubstituted calix[4]arene (2). Second substitution was achieved by the reaction of 2 with various acyl chlorides. Aminomethylation of monobenzoylated calix[4]arene was conducted successfully in the presence of secondary amine and formaldehyde.

Several ester group-containing calix[4]arenes were synthesized by the reaction of calix[4]arene and various acyl chlorides. Two or four ethyl succinyl units could be introduced into the calix[4]arene lower rim depending on the reaction conditions. But the mixture of three and four ethyl malonyl substituted calix[4]arenes were obtained and only three ethyl oxalyl units were introduced at the lower rim of calix[4]arene. Interestingly when calix[4]arene was treated with ethyl oxalyl chloride in the presence of aluminum chloride, two ethyl oxalyl units were introduced at the upper rim of calix[4]arene. The conformation of those ester-containing calix[4]arenes was presented based on the 1H and 13C NMR spectra.

The syntheses and photoreactions of haloarenes, in which the aryl and haloaryl moieties are tethered by a simple alkyl group, were studied. For 2-benzyl-1-halobenzene, in which two aryl moieties were connected by methylene group, photoreduced product, diphenylmethane, was obtained along with the minor formation of the photocyclized product, fluorene, in acetonitrile solvent. For 1-halo-2-phenethylbenzene, in which two aryl moieties were connected by ethylene group, photocyclized products, 9,10-dihydrophenanthrene and phenanthrene, were obtained along with the minor formation of photoreduced product, bibenzyl, in acetonitrile solvent. The photoreaction selectivities in several solvent systems were studied: In cyclohexane, 2-benzyl-1-chlorobenzene was photoreduced more effective than 2-benzyl-1-bromobenzene; In the presence of NaOH, 1-halo-2-phenethylbenzenes gave 9,10-dihydrophenanthrene and, in the presence of toluene, they gave phenanthrene. A radical reaction mechanism is proposed for the explanation of the reactions. This study shows that the photoreaction of haloarene, in which haloaryl and aryl moieties are tethered by ethylene group, can be used for ring formation of 9,10-dihydrophenanthrene otherwise difficultly accessible.

The interactions between Ln(dpm)3 [Ln3+=Eu3+, Yb3+, Pr3+, Sm3+, Tb3+and Ho3+; dpm=tris 2,2,6,6-tetramethylheptane-3,5-dionate] and acetamide in CCl4 solution were investigated using near IR absorption spectroscopy. From the measured 2 νC=O+ amide Ⅲ combination band of acetamide in the region of 2130-2180 nm(4695-4587 cm-1), it was found that acetamide is coordinating through its carbonyl oxygen atom to Ln(dpm)3[C=O…Ln(dpm)3)] and forms only 1 : 1 stoichiometric Ln(dpm)3- acetamide complex. The ΔHo values for the formation of Ln(dpm)3-acetamide obtained from the temperature studies are -39.1, -28.4, -25.5, -24.7, -21.1 and -17.7 kJ mol-1 for Eu(dpm)3, Yb(dpm)3, Pr(dpm)3, Sm(dpm)3, Tb(dpm)3 and Ho(dpm)3, respectively, which are larger than those of the hydrogen bond between amide and various hydrogen acceptors. Except Eu(dpm)3 and Yb(dpm)3, -ΔHovalue increases as the ionic size increases.

Simple conditions were discovered to afford tripyrranes by reaction of 2,5-bis(α-hydroxymethyl)furan or 2,5-bis(α-hydroxy-α-phenylmethyl)thiophene with excess pyrrole in the presence of acid catalyst. Stepwise synthesis of porphyrins with core-ligand modification and synthesis of meso-tetraarylporphyrins bearing two different substituents in cis orientation have developed as building blocks for the various porphyrin-based model systems. Consequently, 21-thia-23-oxa-10,15-diphenylporphyrin (28), 21-oxa-10,15-diphenylporphyrin (29) and 21-oxa-23-carba-12-aza-10,15-diphenylporphyrin (30) were synthesized by acid-catalyzed [3+1] condensation between tripyrranes and 2,5-bis(α-hydroxymethyl)pyrrole or 2,5-bis(α-hydroxy-α-phenylmethyl)thiophene. The synthetic pathway described here gave regioisomerically pure porphyrins and thus overcame the synthetic problems associated with separation and purification of regioisomeric mixture.

Solvolyses of phenyl chloroformate in water, D2O, CH3OD, 50% D2O-CH3OD, and in aqueous binary mixtures of acetone, ethanol and methanol are investigated at 25.0 ℃. Product selectivities are reported at 25 ℃ for a wide range of ethanol-water and methanol-water solvent compositions. The Grunwald-Winstein plots of first-order rate constants for phenyl chloroformate with YCl (based on 2-adamantyl chloride) show marked dispersions into three separate lines for the three aqueous mixtures with a small m value (m< 0.2) and a rate maximum for aqueous alcohol solvents. Third-order rate constants, kww, kaw, kwa and kaa were calculated from the observed kww and kaa values together with kaw and kwa calculated from the intercept and slope of the plot of 1/S vs. [alcohol]/[water]. The calculated rate constants, kcalc and mol % of ester agree satisfactorily with those of the observed rate constants, kobs and mol % of ester, supporting the stoichiometric solvation effect analysis. The kinetic solvent isotope effects determined in water and methanol are consistent with the proposed mechanism of the general base catalyzed and/or carbonyl addition for phenyl chloroformate solvolyses based on mass law and stoichiometric solvation effect studies.

Seven cali[4]arenes, having two different substituents in AAAB or AABB pattern at the upper rim of calix were synthesized by fragmentation condensation reaction of p-substituted phenol trimer (AAA) with 2,6-bishydroxymethylated 4-substituted phenol (B) or that of dimer (AA) with 2,2'-bishydroxymethylated dimer (BB). An equimolar mixture of the coupling components (trimer and monomer or dimer and dimer) was refluxed in dioxane in the presence of TiCl4to afford calix[4]arene 6 and 7 in 15-38% yield. The structure of calix[4]arenes was confirmed by elemental analysis and the 1H/13C NMR spectroscopy.

Muricellaxanthin, a novel carotenoid pigment has been isolated by activity-guided separation from an undescribed gorgonian of the genus Muricella collected from Jaeju Island. Structure of this compound has been determined by a combination of spectral methods. Stereochemistry has been defined by interpretation of nOe data and comparison of CD data with related compounds. Muricellaxanthin exhibited potent lethality against brine-shrimp larvae.

The bulk photopolymerization of methacrylic acid (MA) with secondary silanes such as PhMeSiH2 and Ph2SiH2 gave poly(MA)s possessing the secondary silyl moiety presumably as an end group. It was found that while the polymerization yields and intrinsic viscosities decreased, the TGA residue yields and the relative intensities of SiH IR stretching bands increased with increasing mole ratio of the secondary silane over MA. The sterically less bulky silane PhMeSiH2 produced poly(MA)s with somewhat higher molecular weights and with similar TGA residue yields compared with the sterically bulkier silane Ph2SiH2. The secondary silanes seem to significantly influence on the photopolymerization of MA as both chain initiation and chain transfer agents.