Mechanisms of the reactions of substituted iso-quinoline and quinoline N-oxides with arenesulfonyl chlorides

The rearrangements of substituted iso-quinoline and quinoline N-oxides with arenesulfonyl chlorides have been carried out to clarify the mode of migration of the arenesulfonoxy group by means of both ¹⁸O tracer and kinetic experiments. In the rearrangements of N-arenesulfonoxy-iso-carbostyril and carbostyril, the main migration route of the arenesulfonoxy group is via the solvent separated ion pair path with a minor portionpassing throug step appears to be N---O bond cleavage. For 1-amino-iso-quinoline N-oxide the migration of tosyloxy group to 1-amino-4-tosyloxyiso-quinoline through the oxygen-bridged ion pair pathway is so fast that the presence of the anhydro base cannot be detected. Reaction of 2-aminoquinoline N-oxide to afford 2-amino-6-tosyloxyquinoline which involves migration to a distant position proceeds rapidly, apparently through the solvent separated ion pair path.     

Direct alkenylation of arylamines at the ortho-position

Treatment of magnesium alkylidene carbenoids, which were generated from 1-chlorovinyl p-tolyl sulfoxides with isopropylmagnesium chloride at −78 °C in toluene, with N-lithio arylamines gave ortho-alkenylated arylamines in moderate to good yields. The reaction was found to proceed in a highly stereospecific manner at the carbenoid carbon. This reaction offers a quite novel and direct alkenylation of arylamines at the ortho-position of the aromatic ring.     

Observation of fluidic behavior in a polymethylmethacrylate-fabricated microchannel by a simple spectroscopic analysis

An easy-to-use and low cost microreactor made of polymethylmethacrylate was mechanically fabricated with a microchannel (200 microm x 200 microm). The laminar flow behavior was investigated by visualizing the flow of red and green aqueous solutions. Digitized color images from a CCD camera were analyzed by resolving the color in RGB mode. Numeric data from red and green color components in the images could reveal the fluidic behavior in the microchannel because the spatial spectroscopic information corresponds to the color solution flows. Effects of corner shapes in a turn, flow rate and surface roughness were observed on the mixing of the laminar flows. A right angle turn and unevenness of +/-10% of the inner wall surface almost mixed the two color laminar flows.     

Accumulation of 2,2-difluoroethanol by bacteria

2,2-Difluoroethanol was accumulated by bacteria, giving difluoroacetic acid and so on. The conversion of 2,2,-difluoroethanol to difluoroacetic acid is unusual in a biological system.     

Sensitive and simultaneous determination of HIV protease inhibitors in rat biological samples by liquid chromatography-mass spectrometry

A sensitive and simultaneous liquid chromatographic-mass spectrometric (LC/MS) method for the determination of current four HIV protease inhibitors (PIs), indinavir (IDV), saquinavir (SQV), nelfinavir (NFV) and amprenavir (APV) in rat plasma and liver dialysate by a microdialysis method was described. An isocratic LC/MS method in combination with atmospheric pressure chemical ionization was developed for the determination of these four PIs in biological samples in the same run. The analytes including an internal standard were extracted from 100 microL of plasma or 150 microL of liver dialysate samples by salting-out with 100 microL of ice-cold 2 M K(3)PO(4) followed by ether extraction. The separation of analytes was carried out on a reversed-phase semi-micro column using 50% of acetonitrile containing 1% acetic acid as mobile phase at a flow rate of 0.2mL/min(-1). The separation was completed within 5 min. Precision, recovery and limits of detection indicated that the method was suitable for the quantitative determination of these PIs in rat plasma or liver dialysate. This simple, sensitive and highly specific LC/MS method is suitable for pharmacokinetic studies and therapeutic drug monitoring in AIDS patients who receive double protease therapy.     

Bismuth triflate-chiral bipyridine complexes as water-compatible chiral Lewis acids

[reaction: see text] Catalytic asymmetric hydroxymethylation of silicon enolates with an aqueous formaldehyde solution has been developed using a chiral bismuth complex. This is the first example of highly enantioselective reactions using a chiral bismuth catalyst in aqueous media. In this paper, we have added Bi(OTf)(3)-1 complex as a "water-compatible Lewis acid". Bi(OTf)3 is unstable in the presence of water but is stabilized by the basic ligand.     

New,convenient synthesis of 2-alkyl- and 2-vinylpyrazolo[3,4-d]-pyrimidine derivatives

Treatment of 1,3-dimethyl-6-hydrazinouracil with the appropriate dimethylformamide dialkylacetal afforded the, corresponding 2-alkyl-5,7-dimethylpyrazolo[3,4-d]pyrimidine-4,6-(5H,7H)diones. The reaction of 1,3-dimethyl-6-(α-methylbenzylidenehydrazino)uracils with dimethylformamide dimethylacetal or triethyl orthoformate gave the corresponding 5,7-dimethyl-2-vinylpyrazolo[3,4-d]pyrimidine-4,6(5H,7H)diones, respectively. Similarly, treatment of 1,3-dimethyl-6-(α-methylbenzylidenehydrazino)uraeils with triethyl orthopropionate yielded the corresponding 5,7-dimethyl-3-ethyl-2-vinylpyrazolo[3,4-d]pyrimidine-4,6(5H,7H)diones.     

Synthesis and structures of one- and two-electron oxidized forms of bis(acetylene)tetrairon clusters Cp'(4)Fe(4)(HCCH)(2) (Cp' = Cp,eta5-C(5)H(4)Me)

Air-oxidation of Cp'(4)Fe(4)(HCCH)(2) (Cp' = Cp (1a), C(5)H(4)Me (1b)) in an NH(4)PF(6)/CH(3)CN solution afforded the one-electron oxidized clusters [Cp'(4)Fe(4)(HCCH)(2)](PF(6)). Oxidation of 1a with excess AgBF(4) in THF afforded [1a](BF(4)), while that of 1b with excess AgBF(4) gave [1b](BF(4))(2). The X-ray crystal structure analysis of [1a](BF(4)) revealed that the monocationic cluster retains the butterfly-type Fe(4)(mu4-eta(2):eta(2):eta(1):eta(1)-HCCH)(2) framework similar to that of the neutral cluster. The average Fe-Fe bond length is shorter by 0.029 A than that in the neutral cluster. Electrochemical oxidation of 1a and 1b in 0.1 M NH(4)PF(6)/CH(3)CN solution at +0.30 and +0.25 V versus Ag/10 mM AgNO(3), respectively, afforded the two-electron oxidized clusters [1a](PF(6))(2) and [1b](PF(6))(2). The X-ray crystal structure analysis for [1b](BF(4))(2) shows that the butterfly-type cluster core is retained but shrinks more of those of neutral and monocationic clusters. The four Fe-Fe bonds in [1b](BF(4))(2) are unequivalent: one Fe-Fe bond (2.397(1) A) is apparently shorter than the others (2.439(2)-2.461(2) A).     

Estimation of the critical micelle concentrations and the aggregation numbers of sodium alkyl sulfates by capillary-type isotachophoresis

The analytical procedure for the separation and quantification of bulk and micellar phases for sodium alkyl sulfates has been investigated by a capillary-type isotachophoresis using a potential gradient detector. Monomer solutions were distinguished from micellar solutions at pH 5.5–6.0; hydrochloric acid — L-Histidine mixture was used as the leading electrolyte and 2-(N-Morpholino) ethanesulfonic acid as the terminating electrolyte.The potential unit value (PU value) due to the monomer solutions was larger than that due to the micellar solutions. The zone length due to monomer solutions increased with increasing concentration of surfactant until a given concentration (CMC); beyond this point the values became constant. On the other hand, the zone length due to micellar solutions increased from this point. We report an applicability of capillary-type isotachophoresis to determination of the CMC's and aggregation number for various sodium alkyl sulfates.     

Fast 5d → 4f luminescence of Pr in Lu2SiO5 single crystal host

Absorption and photoluminescence spectra including the decay kinetics of the Pr³⁺-doped Lu₂SiO₅ were measured. Fast luminescence originating from the radiative 5d → 4f transition of Pr³⁺ center is revealed with the maximum at 273 nm at room temperature. Low temperature photoluminescence decay is governed by the 25 ns decay, while substantial shortening to 6–7 ns occurs at room temperature. With the help of slow decay measurement in the millisecond time scale we evidence the thermal ionization of the relaxed excited 5d₁ state of Pr³⁺. The ionization can explain the observed temperature dependences of the decay times and emission intensity.