Stereoselective nucleophilic addition reactions to nitro sugars

Nucleophile(s) almost exclusively added from the equatorial side of 2-nitro-β-$\text{D}$-2-enopyranoside and the axial side of 2-nitro-$\text{D}$-$\text{ribo}$-1-enitol. On the other hand, methoxide and $\text{tert}$-butyl peroxide ions approached from the equatorial side of 2-nitro-α-$\text{D}$-2-enopyranoside, whereas methanol and hydrogen peroxide ion from the axial side.     

Determination of urea by ion chromatography with an immobilized urease reactor

An immobilized urease reactor can be used with ion chromatography for the simultaneous determination of urea, and sodium, potassium and ammonium ions. The conversion of urea to ammonium ion was found to be 76.5%. The calibration graph for urea was linear over the range 1 × 10^?5?1 × 10^?3 M (RSD 3%). The method was applied to human urine and a chemical fertilizer.     

Stereochemistry of nucleophilic addition reactions 13 : Kinetically controlled nucleophilic addition reactions to methyl 4,6-0-benzylidene-2,3- dideoxy-2-nitro-β-D-erythro-hex-2-enopyranoside: an important role of a(1,3) strain

An improved synthesis of methyl 4,6-0-benzylidene-2,3-dideoxy-2-nitro-β-D-erythro-hex-2-enopyranoside and its reactions with various nucleophiles are described; all the nucleophiles were found to approach exclusively or predominantly from the equatorial side of the molecule, giving the β-D-glucopyranoside derivatives as the major or exclusive product. The stereochemical course of approach of a nucleophile observed in the present reactions and in the literature are discussed.     

The flameless atomic absorption spectrometric determination of aluminum with a carbon atomization system

The atomic absorption spectrometry of aluminum with a carbon tube atomizer is described, with particular reference to the heating cycle, argon flow rate and amplifier time constant. Interferences are eliminated by pre-atomization heating or with a hydrogen-argon-entrained air flame. Under optimal conditions, the sensitivity (1 % absorbance) is 5·10^?11g, and the relative standard deviation is 2.3 for 2.5 ng Al.     

Ethenesulfonamide derivatives, a novel class of orally active endothelin-A receptor antagonists

In the present article we wish to report the discovery of a novel class of ET(A)-selective endothelin (ET) receptor antagonists through the modification of the ET(A)/ET(B) non-selective antagonist, Ro47-0203 (Bosentan, 1). Replacement of the benzenesulfonamide group of 1 with a 2-phenylethenesulfonamide group gave compound 5a and resulted in improvement in ET(A)-selectivity. Optimization of the alkoxy side chain attached to the core pyrimidine ring yielded the 2-fluoroethoxy derivative (5n) with further improvement of ET(A)-selectivity. [IC50=2.1 nM for ET(A) receptor, ET(B)/ET(A) ratio=1200]. After oral administration, compound 5n inhibited the big ET-1 induced pressor response in pithed rats with a DR2 value of 2.6 mg/kg and also exhibited a potent antagonistic activity in conscious rats.     

Capillary gas chromatography of lower aliphatic C2?C5 aldehydes in the free form as a group of pungent odorants in air

The capillary gas chromatography of the C₂-C₅ lower aliphatic aldehydes (e.g.,acetaldehyde, propionaldehyde, n- and i-butyraldehydes, n- and i-valeraldehydes) which, in the free form in air, have unpleasant odors and low threshold odor values, has been studied using cold-trap preconcentration with liquid oxygen. The capillary column outlet was connected to enable simultaneous detection by FID, ECD, FPD AND FTD (SID).     

Lewis Acid-Catalyzed Hydrostannation of Acetylenes. Regio- and Stereoselective Trans-Addition of Tributyltin Hydride and Dibutyltin Dihydride

Lewis acids such as ZrCl(4) or HfCl(4) catalyze the hydrostannation of acetylenes 1 by tributyltin hydride to produce the cis vinylstannanes 2 by regio- and stereoselective anti-hydrostannation. The hydrostannation of acetylenes using dibutyltin dihydride was also catalyzed by ZrCl(4) to give the stereodefined Z-Z divinyltin derivatives 4 by an anti-hydrostannation pathway. The use of nonpolar solvents such as toluene or hexane was essential for obtaining high stereoselectivity and chemical yield. Since ZrCl(4) and HfCl(4) are not soluble in such solvents, the hydrostannations were carried out in a heterogeneous system. The reactions of internal acetylenes with Bu(3)SnH proceeded smoothly, although the use of stoichiometric amounts of ZrCl(4) gave better results. The ZrCl(4)-catalyzed hydrostannation at 0 degrees C gave better yields and stereoselectivities than the reaction at room temperature. To help clalify the reason, the reaction of Bu(3)SnH with ZrCl(4) was monitored by (1)H and (119)Sn NMR spectroscopy, and it was found that Bu(3)SnH reacted with ZrCl(4) at room temperature to afford a mixture of tributyltin hydride, dibutyltin dihydride, and tetrabutyltin.     

Total synthesis of slow reacting substances (SRS's): 6-epi-leukotriene C and 6-epi-leukotriene D

6-$\text{Epi}$-leukotrienes C and D (3 and 4) have been synthesized unambiguously via the 5($\text{S}$), 6($\text{R}$)-epoxide (5,6-$\text{cis}$) which is isomeric with leukotriene A. These 6-$\text{epi}$-leukotrienes are less active (especially 4) than leukotrienes C and D (1 and 2) and have not been found in substantial quantity in natural SRS sources.     

Total synthesis of slow reacting substances (SRS). “Leukotriene C-2” (11-trans-leukotriene C) (3) and leukotriene D (4)

Syntheses are described for the “slow reacting substances” 11-$\text{trans}$-leukotriene C (3) (previously known as leukotriene C-2) and leukotriene D (4), the cys-gly analog of leukotriene C (2). The synthesized leukotrienes 3 and 4 were instrumental in the assignment of structure to these members of the family of naturally occuring slow reacting substances which includes also 2.