Micro-phase sorbent extraction for trace analysis via in situ sorbent formation: application to the spectrophotometric determination of nitrite in environmental waters.

A micro-phase sorbent in situ formation from an aqueous solution was proposed for the sensitive spectrophotometric determination of nitrite in environmental waters. Nitrite in a 10 mL sample solution was converted into a cationic azo dye by the reaction with 4-trifluoromethylanilinium ion and N-1-naphthylethylenediammonium ion in an acidic medium. Addition of dodecylbenzenesulfonate ion caused the formation of a suspension of ion associate in the solution. Centrifugation of the solution led to the isolation of a liquid organic phase that extracted the azo dye at the bottom of the centrifuge tube. The volume of the new phase was ca. 5 microL. After the aqueous phase was discarded, the organic phase was dissolved with 1 mL of 2-methoxyethanol to measure the absorbance. Nitrogen as NO2- at concentrations from 1.5 to 30 microg L(-1) was determined with sufficient precision. When 0.2 mL of 2-methoxyethanol was applied to dissolve the organic phase, 0.3-4.8 microg NO2--N L(-1) was determined. The recovery tests for nitrite added to some river water and seawater were satisfactory. This method is very simple and rapid. It takes only 30 min from the dye formation to the measurement of the absorbance.     

Ru(II)-catalyzed chemo- and regioselective cyclotrimerization of three unsymmetrical alkynes through boron temporary tether. One-pot four-component coupling via cyclotrimerization/Suzuki-Miyaura coupling

The Ru(II)-catalyzed [2+2+2] cyclotrimerization of alkynylboronates, propargyl alcohol, and terminal alkynes proceeded chemo- and regioselectively to give rise to arylboronates, which were subjected to Suzuki-Miyaura cross-coupling with aryliodides to afford highly substituted biaryls in 53-76% yields.     

Application of intramolecular 1,3-dipolar cyclic addition of azide and olefin; construction of (pyrrolidine-2-ylidene)glycinate and glycinamides

Oxopropyl E-(pyrrolidine-2-ylidene)glycinamide (5c) and allyl E-(pyrrolidine-2-ylidene)glycinate (5d) were effectively synthesized from 2,3,5-tri-O-benzyl-4-O-tert-butyldimethylsilyl(TBDMS)-D-arabinal (7) using intramolecular 1,3-dipolar cyclic reaction of azide and olefin as a key reaction. These results proved this cyclic reaction should be applicable for the synthesis of various (pyrrolidine-2-ylidene)glycinate and glycinamide. In addition, the development of a synthetic route for the precursor of an unsaturated cyclic dehydro amino acid involved in azinomycins (carzinophilin) using relating glycinate, methyl E-(pyrrolidine-2-ylidene)glycinate (5a) was described.     

Antioxidant effects of hydroxybenzalacetones on peroxynitrite-induced lipid peroxidation in red blood cell membrane ghost and SOS response in Salmonella typhimurium TA4107/pSK1002

Antioxidant activity of a series of hydroxybenzalacetones was determined against peroxynitrite-induced lipid peroxidation in red blood cell membrane and SOS response through DNA damage in bacterial cells. Hydroxybenzalacetone derivatives with hydroxy, methoxy, ethoxy or methyl substitution were analyzed and found to be more effective than the water-soluble vitamin E analogue Trolox. The inhibitory effect against lipid peroxidation correlated well to that against the SOS response, which is dependent on decomposition of peroxynitrite by hydroxybenzalacetones outside of the cell membrane. The antioxidant activity was shown to correlate well with the electric parameter sigma+. Electron-donating substituents with more negative sigma+ values increased the potencies. The result suggests that hydroxybenzalacetones with more electron-donating substituents will protect tissue more effectively against oxidative stress.     

Medium-sized cyclophanes—XVII : Tetra-, hexa-, octa- and decahydropyrenes from [2.2]metacyclophane. Transannular dehydrogenation,isomerization, and disproportionation reactions by means of benzoyl peroxide,metal salts and sulfuric acids

[2.2]Metacyclophane (1) undergoes a variety of reactions according to the reagents and conditions. These include (1) substitution (path a), (2) transannular dehydrogenation (path b and c), (3) cycloisomerization (path d) and (4) transannular hydrogenation. A brief summary of these reactions is presented.The diversity of the reactions of 1 is further explored using benzoyl peroxide (BPO), cupric chloride, aluminum chloride, other metal salts, H₂SO₄ and FSO₃H. With BPO or cupric chloride, one-electron transfer mechanism is postulated. This involves a tautomeric ion pair formed by the intramolecular arylation with an aryl cation radical. A supporting evidence in favor of the mechanism is presented from experiments using various metal salts in different solvents.On the contrary, the reaction with aluminum chloride gives decahydropyrene (8) and octahydropyrene (11) together with cycloisomerization product 5 and dehydrogenation products 2, 3 and 4. When treated with AlCl₃HCl 1 gives similar products as above but the product ratios are quite different. The major product is 5 but only a trace amount of 8 is formed. The reaction with H₂SO₄ or FSO₃H also produce 2, 4, 5 and 11. Some mechanistic evidence in favor of the disproportionation reaction is presented.     

Symmetry or asymmetry in cheletropic additions forming cyclopropanes

Cheletropic additions forming cyclopropane rings were studied theoretically. Ten addition paths were traced by means of density-functional-theory calculations. Two 1,4-dienes, 1,4-pentadiene, and tricyclo[5.3.1.0^4,9]undeca-2,5-diene were adopted as substrates. CO, SO₂, C₂H₅PCl₂, CCl₂ and SiCl₂ were employed as cheletropic reagents (Xs). An orbital correlation diagram of the Woodward–Hoffmann (W–H) rule and frontier molecular orbital (FMO) interactions between them were investigated in detail. The FMO interactions, HOMO (1,4-diene)lumo (X) and homo (X)LUMO (diene), work reasonably for the progress of the reactions. Those cause the formation of two C–X bonds and a cyclopropane ring, and alternation of double bonds to single bonds. All the additions are concerted. The easiness of the ring formation depends upon the energy gap between HOMO and lumo and that between homo and LUMO, and the spatial directions of HOMO and LUMO extensions. Symmetry conservation of the W–H rule does not hold necessarily for those addition paths. The symmetry-breaking was discussed in terms of FMO interactions.Acknowledgement This work was supported by a Grant-in-Aid for Scientific Research from the Ministry of Education, Science and Culture, Japan and by Nishida Memorial Foundation for Fundamental Chemical Research.     

Tertiary amine-mediated synthesis of microporous carbon membranes

Microporous carbon membranes were prepared on an -alumina support by a pyrolysis of cationic tertiary amine/anionic polymer composites. The precursor solutions contain a thermosetting resorcinol/formaldehyde (RF) polymer and a cationic tertiary amine. Three types of cationic tertiary amines with different chain lengths were used, such as tetramethlammonium bromide (TMAB), tetrapropylammonium bromide (TPAB) and cetyltrimethylammonium bromide (CTAB). A porous structure was produced by a decomposition of the amine and the resulting pores assisted the further gasification of the RF polymer at high temperature. The carbon/alumina membranes have thin and continuous carbon top layers with a thickness of 1 μm. Gas permeation tests were performed using single gases of CO₂, O₂, N₂, CF₄, n-C₄H₁₀ and i-C₄H₁₀, as well as binary mixtures of CH₄/n-C₄H₁₀ and N₂/CF₄ at different temperatures between 23 and 150 °C. The carbon membrane prepared using TMAB showed separation factors higher than 650 for the CH₄/n-C₄H₁₀ mixtures and higher than 8100 for the N₂/CF₄ mixture. From the permeation of pure gases with different molecular sizes, the pore sizes of the carbon membrane prepared using TMAB, TPAB and CTAB are estimated to be 4.0, 5.0 and larger than 5.5 Å, respectively, indicating that the micropore size of the carbon membranes is controllable by using different amines.     

Electrophoretic analysis of quinone anion radicals in acetonitrile solutions using an on-line radical generator

We have investigated analysis of anion radicals of phenanthrenequinone (PhQ) and anthraquinone (AQ) using acetonitrile-capillary electrophoresis (CE) under anaerobic conditions. PhQ and AQ have relatively high negative reduction potentials meaning that their anion radicals are re-oxidized quite readily by the surrounding O(2) to disappear during analysis and we failed to detect them with our previous system. In this work, we have developed an on-line system combining a unique electrolysis cell for generation of the radicals and a CE unit to keep the analysis system free from external O(2) molecules and to reduce analysis time remarkably. As a result, electrophoretic detection of the anion radicals of PhQ and AQ has been achieved. Furthermore, we have observed hydrogen-bonding interaction between the anion radicals and dimethylurea (DMU) using the present system and have indicated a characteristic interaction of the anion radical of PhQ as an ortho-quinone with DMU.     

Synthesis and spectral behavior of 5-methyl-3-phenyl-1,3-oxazolidin-2-ones using NMR

Heterocyclic compounds of four 5-methyl-3-phenyl-1,3-oxazolidin-2-ones have been synthesized by the reaction of N-2-hydroxyethyl- or N-2-hydroxypropylanilines with phosgene in the presence of pyridine. From the spectral behavior, the title compounds are found to exist in the trans and cis forms.