Making the liquid-phase catalytic hydrodechlorination of pce over Pd/C safer

Summary The hydrodechlorination of tetrachloroethylene in methanol (MeOH) over palladium catalysts on activated carbon (Pd/C) at 20°C and atmospheric pressure was rendered safer by using ethanol (EtOH), isopropanol (IPA) or water-alcohol mixtures as solvents. Adding water to MeOH was better than using EtOH or IPA since it resulted in a faster reaction and better stability of Pd/C, which could also be completely reactivated.     

Phenolic constituents of licorice. III. Structures of glicoricone and licofuranone, and inhibitory effects of licorice constituents on monoamine oxidase

Two new phenolic compounds, glicoricone (3) and licofuranone (4), were isolated from a species of licorice brought from the northwestern region of China, and their structures were assigned. Among the twelve licorice constituents examined for the inhibition of monoamine oxidase (MAO), six compounds, 3, 4, genistein (6), licopyranocoumarin (7), licocoumarone (14) and glycyrrhisoflavone (15), inhibited the enzyme with the IC50 (concentration required for 50% inhibition of the enzyme activity) values of 6.0 x 10(-5)-1.4 x 10(-4) M. Glycyrrhizin (1) also inhibited MAO with the IC50 value of 1.6 x 10(-4) M.     

A versatile method for preparation of O-alkylperoxycarbonic acids: epoxidation with alkyloxycarbonylimidazoles and hydrogen peroxide

A variety of O-alkylperoxycarbonic acids ($\text{2}$) were conveniently prepared $\text{in}$$\text{situ}$ by utilizing alkyloxycarbonylimidazoles ($\text{1}$) as their precursors. Epoxidation of alkenes with such peroxy-acids was studied and their reactivities were compared with those of peroxycarboxylic acids.     

Mechanism of plasma-initiated polymerization: Concerning the nature of solvent effects on the lifelike polymerization of water-soluble vinyl monomers

To provide a satisfactory basic understanding of the solvent effect of plasma-initiated polymerization, we have carried out several kinds of polymerizations of various water-soluble vinyl monomers. It has been shown that aqueous solution of such vinyl monomers underwent the polymerizations induced by methyl isobutyrate (MIB) plasma-exposed glass surface. The invisible ultrathin polymer film trapping an active radical species deposited on the plasma-exposed glass surface apparently induced the polymerizations. The efficiency, however, was largely dependent on the solvent used: the solvent can be considered to act as “an initiation-activator” for the lifelike postpolymerization. The nature of the solvent effect was ascribed to the physicomechanical property such as swelling ability and/or solubility toward the ultrathin film formed on the glass surface. Thus it has been suggested that the choice of good-balanced combination between the structural feature of the plasma-induced ultrathin polymer film and the solvent as an initiation-activator is important to achieve activity of a desired solution polymerization.     

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.     

Recognition of chiral catechols using oxo-titanium phthalocyanine

Oxo-titanium phthalocyanine (TiOPc) derivatives of catechin and hematoxylin (natural ortho-diol type chiral compounds) have been prepared and characterized by spectral and chromatographic techniques. It is demonstrated that the TiOPc unit is an excellent template for chiral recognition through its isolated Q-transitions. The formation of a helical dimeric complex with hematoxylin induces strong CD-activity in the Q-band region. Ab initio geometry optimizations were combined with a Kuhn-Kirkwood coupled-oscillator mechanism to obtain the absolute configuration of hematoxylin. In addition, it is shown that the described chiroptical recognition method is sensitive to slight conformational changes.     

A High Sensitivity Fluorescent Chemo-sensory System Based on β-Cyclodextrin Dimer Modified with Dansyl Moieties

-Cyclodextrin dimer linked with ethylenediamine at the upper rim of the cyclodextrin has been synthesized and then modified with two dansyl moieties inthe presence of N,N'-dicyclohexylcarbodiimide. The sensing ability and bindingproperty of the title compound were investigated for steroids and terpenoids. Thefluorescence intensity of this dimer was decreased when a host–guest complex was formed. The value I/I⁰, where I⁰ and I are fluorescence intensitiesin the absence and presence of a guest and I is I⁰- I, was used as a parameter of sensitivity. This host exhibited a much higher sensitivity and selective molecular recognition ability for bile acids such as ursodeoxycholic acid andchenodeoxycholic acid and terpenoids such as (-)-borneol than the dansyl-modifiedcyclodextrins reported previously including -cyclodextrin dimer. The behaviors of the appended moieties of the host during the formation of host–guest complexes were studied using induced circular dichroism (ICD) and fluorescence spectra. The ICD intensityof this dimer was decreased on accommodation of a guest and this spectral pattern of the title dimer was opposite to that of bis dansyl-modified -cyclodextrin monomer. Theguest-induced variations in the fluorescence and ICD intensities suggest that this dimer formed a 1 : 1 host–guest complex and the appended moieties act as a hydrophobic cap.     

A novel acid-catalyzed rearrangement of n-aryl-n′-aryloxyureas to biphenyl derivatives. A [5,5]-rearrangement involving three heteroatoms.

In the presence of trifluoroacetic acid, N-phenyl-N′-phenoxyurea (1a) rearranges to N-(4′-hydroxy-2-biphenylyl)urea (2a) and N-carbamoyl-2-hydroxy-diphenylamine (3a). The rearrangement is an intramolecular reaction, and the transition state of the breakage of the N-O bond is deduced to be polarized in the form N^δ- --- O^δ+. The reaction is entirely new and constitutes a fundamental aromatic rearrangement.     

Mixed-valence state of optically active 1',1'"-bis(2-phenylbutyl)-1,1''-biferrocenium pentaiodide: effects of cation symmetry and intermolecular interaction on trapped-/detrapped-valence states

The effects of cation symmetry and packing on the mixed-valence state of binuclear ferrocene derivatives are discussed separately by using chiral isomers and racemic modification of 1',1' "-bis(2-phenylbutyl)-1,1' '-biferrocenium pentaiodide. The pentaiodide anion has a polymeric structure and is composed of triiodide anion and iodine molecule units. The (R,S) isomer having an inversion center shows a detrapped-valence state even at 78 K. On the other hand, the (R,R) and the (S,S) isomers having no inversion center show a trapped-valence state at room temperature. The racemic modification, however, consisting of the (R,R) and the (S,S) isomers shows a perfect detrapped-valence state at room temperature. This finding shows that the packing effect overcomes the effect of cation asymmetry.