Design of a new molecule that exhibits observable CD spectra under σ-σ* excitation: 2,6-Disilyl-2,6-disilaspiro[3.3]heptanes

Abstract

We previously designed and prepared the first molecules to exhibit observable CD spectra by n-σ* excitation, 2,6-dithiaspiro[3.3]heptane 2,6-dioxide. Spiro[3.3]heptane frameworks possess axial asymmetry due to puckering of 2 four-membered rings; the ring bonds are rich in p-character due to acute bond angles, which lowers the σ* energy levels. In contrast, the lone pairs are rich in s-character, which results in a good donor with conformational fixation. We expected that, instead of lone pairs as donating orbitals, the use of σ-electron-donating Si-Si bonds should result in UV absorption in the observable range (>180?nm), so that the Cotton effect could appear, at least partially, in that range. We designed 2,6-disilyl-2,6-disilaspiro[3.3]heptanes as models, and performed theoretical calculations to confirm our idea.     

Synthesis and Odor Evaluation of Stereoisomers of Imine Derivatives in Roasted Spotted Shrimp

All possible stereoisomers of imine derivatives 1 – 4 , which have the characteristic roast odor of seafood, were synthesized. As a result of odor evaluation of all isomers, we found that each isomer has a different and characteristic odor of roasted seafood.     

Substituent effects on the tautomer ratios between the hydrazone imine and diazenyl enamine forms in side-chained quinoxalines

The 3-(arylhydrazono)methyl-2-oxo-1,2-dihydroquinoxalines 9–11 were synthesized by the reaction of the quinoxalines 6–8 with various p-substituted benzenediazonium salts. Compounds 9–11 showed the tautomeric equilibria between the hydrazone imine A and diazenyl enamine B forms in dimethyl sulfoxide media. The substituent effect on the tautomer ratios of A to B was studied by the nmr spectroscopy to clarify that the presence of the ester group R² on the hydrazone carbon and electron-donating p-substituent R¹ on the side chain benzene ring exhibited a tendency to increase the ratios of the tautomer A .     

CHOICE OF COATINGS FOR THE OPTICAL ELEMENTS IN THE IRRADIATION SYSTEM OF VACUUM-ULTRAVIOLET RADIATION ABOVE 50 nm

The spectral throughput of a vacuum-ultraviolet irradiation system at the SOR-RING facility was examined with various combinations of aluminum-and gold-coated optical elements in a 2.2-m modified Wadsworth monochromator. We found that the optimum was a combination of an aluminum-coated collimating mirror, concave grating, and plane deflecting mirror, and a combination of a gold-coated collimating mirror, concave grating and an aluminum-coated plane deflecting mirror in the wavelength regions 190-110 nm and 110-50 nm, respectively.     

Synthesis,structure, and dynamic behavior of cyclopentadienyl-lithium, -sodium,and -potassium annelated with bicyclo[2.2.2]octene units: a systematic study on site exchange of alkali metals on a cyclopentadienyl ring in tetrahydrofuran

Novel cyclopentadienyl (Cp)-alkali metal complexes 1-M and 2-M (M = Li, Na, K), in which the Cp ring is annelated with two bicyclo[2.2.2]octene units and substituted with a phenyl group for 1 and a tert-butyl group for 2, were synthesized, and their structures and dynamic behaviors were investigated by means of X-ray crystallography, dynamic (13)C NMR, and DFT calculations. The X-ray crystallography results indicated that 1-Li, 1-Na, and 2-Na form monomeric contact ion pairs (CIP) with three THF molecules coordinated to the metal atom. Also, in THF-d(8), all of the 1-M and 2-M form monomeric CIP in the ground state. However, variable-temperature (13)C NMR measurements of 1-M and 2-M in THF-d(8) demonstrated dynamic behavior in which the metal ion exchanges positions between the upper and lower faces of the Cp ring. From a study of the concentration dependence of the dynamic behavior, the exchange was found to proceed principally as an intramolecular process at concentration ranges lower than 0.2 M. The experimentally observed deltaG values for the intramolecular exchange process for all the 1-M and 2-M (except for 2-Li, whose intramolecular process was too slow to observe) were found to be quite similar in THF-d(8) solution and to fall within the range of 12-14 kcal mol(-)(1). Within this range, a tendency was observed for the deltaG values to increase as the size of the metal decreased. Theoretical calculations (B3LYP/6-31G(d)) afforded considerably large values as the gas-phase dissociation energy for 1-M (162.7 kcal mol(-)(1) for M = Li; 131.6 kcal mol(-)(1) for M = Na; 110.9 kcal mol(-)(1) for M = K) and for 2-M (170.0 kcal mol(-)(1) for M = Li; 137.5 kcal mol(-)(1) for M = Na; 115.4 kcal mol(-)(1) for M = K). These values should be compensated for by a decrease in the solvation energies for the metal ions with increasing size, as exemplified by the calculated solvation energy for M(+)(Me(2)O)(4), which serves as a model for metal ions solvated with four molecules of THF (-122.9 kcal mol(-)(1) for M = Li; -94.7 kcal mol(-)(1) for M = Na; -67.7 kcal mol(-)(1) for M = K). This compensation results in a small difference in the overall energy for dissociation of 1-M or 2-M in ethereal solutions, thus supporting the similar deltaG values observed for the intramolecular metal exchange.     

Phase Separation in Sol-Gel System Containing Mixture of 3- and 4-Functional Alkoxysilanes

The phase separation behavior of gelling systems containing the mixture of 3-functional and 4-functional alkoxysilanes has been investigated. The relation between the starting composition and resultant macroporous morphology was examined using tetramethoxysilane (TMOS) and vinyltrimethoxysilane (VTMS) as starting alkoxysilanes, formamide (FA) as an additive, under an acidic condition. Up to TMOS:VTMS molar ratio of 0.5:0.5, the phase relation remained almost unchanged from that of pure TMOS system which exhibits morphology with well-defined co-continuous macropores in a very limited concentration region. On the VTMS-rich side typically TMOS:VTMS = 0.2:0.8, however, the co-continuous macroporous morphology was obtained in a broader composition range than those of either pure TMOS or VTMS system. A dome-like pseudo binary region was obtained with the two-phase region extending toward FA-rich direction. The domain size and pore volume of the gels with macroporous morphology could be controlled by alkoxide:water ratio and total solvent fraction, respectively.     

A regio- and stereoselective alpha-methylation of gamma,delta-epoxy-alpha,beta-unsaturated esters with a Me2Zn-CuCN reagent

A highly regio- and stereoselective alpha-methylation reaction of gamma,delta-epoxy-alpha,beta-unsaturated esters was achieved by using a Me2Zn-CuCN reagent.     

Selective desorption and analysis of humic substances on suspended particles in river water

The elemental analysis and morphology of individual particles indicate that the dominant suspended particles in river water are kaolin covered with hydrated iron(III) oxide which strongly sorbs humic substances. Suspended particles, about 1 mg, collected from 250 ml of water by centrifugation, are treated with 0.7 ml of 0.1M sodium hydroxide to desorb humic substances. Approximately 60% of copper and 30% of lead on or in suspended particles exist as humic complexes.     

Preconcentration of Trace Elements in Water for Speciation Studies

Trace element speciation has recently become one of the most important problems in water analysis. Proper combination of preconcentration techniques with instrumental determination methods is essential to speciation analysis, because sensitivity and selectivity of direct determination methods are generally lacking. The present paper describes such preconcentration techniques as filtration, centrifugation, flotation and sorption, which have been developed in the author's laboratory for the speciation of heavy metals in river and pond waters by electron microscopy, X-ray microanalysis and chemical analysis. The application of freeze concentration to the speciation of silica in high-purity waters is also discussed.