Spectrophotometric determination of ascorbic acid with potassium hexacyanoferrate(III)

A new, simple and rapid method of determination of ascorbic acid in amounts of 45-360 mug is described. The ascorbic acid is determined spectrophotometrically at 420 nm from the decrease in absorbance it causes in 1 x 10(-3)M hexacyanoferrate(III) in McIlvaine buffer at pH 5.2. The proposed method is suitable for the determination of ascorbic acid in pharmaceutical preparations and probably natural products.     

On the reaction of isothiosemicarbazides with heterocumulenes. Part I

Isothiosemicarbazides 2 react with acyl isothiocyanates under addition-cyclization to yield 1,3,4-thiadiazoline-2-imines 3 as well as the isomeric 2-amino-substituted 1,3,4-thiadiazolium-5-acylaminides 3′ . In a similar manner the 2-hydrazino-substituted 1,3-thiazoline 4 adds ethoxycarbonyl isothiocyanate to give the thiosemicarbazide 5 , which undergoes a rearrangement to the 1,3,4-thiadiazoline-2-imine 5′. The [2+2] cycloreversion of 3d involving ethoxycarbonyl iso(thio)cyanate and the thermal induced Dimroth rearrangement of 3′f and h are also discussed.     

Ultra-trace analysis of U,Th, Ca and selected heavy metals in high purity refractory metals with isotope dilution mass spectrometry

A method for the determination of trace impurities (U, Th, Ca, Fe, Cr, Ni, Cu, and Cd) in the refractory metals molybdenum and tungsten with isotope dilution mass Spectrometry (IDMS) has been developed. This method enables determinations of uranium and thorium down to the lowest pg/g level with high precision and accuracy. Selective chromatographic, extractive and electrolytic methods for the trace-matrix separation were combined with positive thermal ionization mass spectrometry. Different samples of high purity (4N) and of ultra high purity (UHP) materials for advanced technologies were analysed. The detection limits reached are (in ng/g): U 0.006, Th 0.008, Ca 10, Fe 19, Cr 0.5, Ni 0.6, Cu 2.7, and Cd 0.12. A comparison of results with other sensitive analytical methods (ICP-MS, GDMS, SIMS) makes obvious the urgent necessity of a reliable calibration method like IDMS because the analytical results obtained by the other methods often spread over a wide range.     

Separation of potential flavoring compounds by high-performance liquid chromatography

High-performance liquid chromatography separated successively and quantitatively the food flavoring agents pyrimidines, purines and nucleosides, followed by nucleotides, then by polyphenols and finally by pyrazines with a reversed-phase octadecylsilica (μBondapak C₁₈) column and various proportions of methanol, water, acetic acid and tetrabutylammonium phosphate (PIC A). The polar solvent (solvent A) was water—acetic acid—PIC A (97.5:1.5:1.0) and the relatively non-polar solvent (solvent B) was methanol—acetic acid—PIC A (97.5:1.5:1.0). Purines, pyrimidines, and nucleosides were eluted with solvent A. Nucleotides were eluted with a mixture of solvents A and B (9:1). Polyphenols were separated with a gradient starting at 10% solvent B and finishing at 25% solvent B, and finally the pyrazines were removed successively from the column with a gradient starting at 25% solvent B and finishing at 45% solvent B. The resolution and reproducibility were excellent for more than 50 compounds. By this method beverages could be analyzed directly, without solvent extraction, for flavoring compounds.     

Novel metathesis catalysts based on ruthenium 1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidenes: synthesis, structure, immobilization, and catalytic activity

The synthesis of novel ruthenium-based metathesis catalysts containing the saturated 1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene ligand, that is, [RuCl2(NHC)[=CH-2-(2-PrO)-5-NO(2)-C6H3]] (1) and [Ru(CF3COO)2(NHC)[=CH-2-(2-PrO)-5-NO2-C6H3]] (2) (NHC=1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene) is described. Both catalysts are highly active in ring-closing metathesis (RCM) and ring-opening cross-metathesis (ROCM). Compound 1 shows moderate activity in enyne metathesis. Compound 2 is not applicable to enyne metathesis since it shows high activity in the cyclopolymerization of diethyl dipropargylmalonate (DEDPM). Poly(DEDPM) prepared by the action of 2 consists of 95% five-membered rings, that is, poly(cyclopent-1-enevinylene)s, and 5 % of six-membered rings, that is, poly(cyclohex-1-ene-3-methylidene)s. The polymerization proceeds in a nonliving manner and results in polyenes with broad polydispersities (1.9< or =PDI< or =2.3). Supported analogues of 2 were prepared by immobilization on hydroxymethyl-Merrifield resin and a monolithic support derived from ring-opening-metathesis polymerization (ROMP). Catalyst loadings of 1 and 2.5%, respectively, were obtained. Both supported versions of 2 showed excellent reactivity. With 0.24-2% of the supported catalysts, yields in RCM and ROCM were in the range of 76-100%. Leaching of ruthenium was low and resulted in Ru contaminations of the products of less than 0.000014% (0.14 ppm).     

Nucleophilic Addition of CH, NH, and OH Bonds to the Phosphadiazonium Cation and Interpretation of (31)P Chemical Shifts at Dicoordinate Phosphorus Centers

The phosphadiazonium cation [MesNP](+) reacts quantitatively with the fluorenylide anion, MesNH(2), and MesOH (Mes = 2,4,6-tri-tert-butylphenyl), resulting in formal insertion of the N-P moiety into the H-Y (Y = C, N, O) bonds. Specifically, reaction of MesNPCl with fluorenyllithium gives the aminofluorenylidenephosphine [crystal data: C(31)H(38)NP, monoclinic, P2(1)/c, a = 9.568(8) ?, b = 24.25(2) ?, c = 11.77(1) ?, beta = 101.38(8) degrees, Z = 4]. Similarly, reaction of [MesNP][GaCl(4)] with MesNH(2) gives the diaminophosphenium salt [MesN(H)PN(H)Mes][GaCl(4)] [crystal data: C(36)H(60)Cl(4)GaN(2)P, monoclinic, C2/c, a = 24.921(2) ?, b = 10.198(4) ?, c = 16.445(2) ?, beta = 93.32(1) degrees, Z = 4], and reaction with MesOH gives the first example of an aminooxyphosphenium salt [MesN(H)POMes][GaCl(4)]. It is proposed that the reactions involve nucleophilic attack at phosphorus followed by a 1,3-hydrogen migration from Y to N. Experimental evidence for the formation of sigma-complex intermediates is provided by the isolation of [MesNP-PPh(3)][SO(3)CF(3)] [crystal data: C(37)H(44)F(3)NO(3)P(2)S, triclinic, P&onemacr;, a = 10.663(1) ?, b = 19.439(1) ?, c = 10.502(1) ?, alpha = 103.100(7) degrees, beta = 113.311(7) degrees, gamma = 93.401(7) degrees, Z = 2]. As part of the unequivocal characterization of the aminooxyphosphenium salt, detailed solid-state (31)P NMR studies and GIAO calculations on the phosphenium cations have been performed. Contrary to popular belief, the phosphorus shielding in dicoordinate cations is not caused by the positive charge but results from efficient mixing between the phosphorus lone pair and pi orbitals.     

Verhalten von ng- und μg-Mengen biochemisch interessierender Amine bei Trennverfahren,wie Ionenaustausch-Chromatographie,Mitfällung und Extraktion

The behaviour of ng- and μg-amounts of amines of biochemical interest is compared. ng-amounts are co-precipitated from aqueous solutions with the tetraphenyloborates of potassium, ammonium and creatinine. A separation from potassium chloride, ammonium chloride and creatinine is achieved by extraction of the amines with methanol. The elution volumes of about 50 amines during ion-exchange chromatography using a weakly acidic resin are compared. A procedure has been elaborated by which the amines can be collected from urine.     

Zur Darstellung von Oxiden cyclischer,sekundärer Arsine

Hydrolysis of 1-chloro-arsolane, C₄H₈AsCl, and 1-chloro-arsenane, C₅H₁₀AsCl, leads to oxides C₈H₁₀As₂O and C₁₀H₂₀As₂O, respectively. On direct alkylation of arsenic trioxide with 1.4-butane- and 1.5-pentane-bis-magnesium bromide these oxides are formed only in trifling amounts. Better results are gained by alkylation of N,N-dimethylaminodichloroarsane into amino-arsolane and amino-arsenane, which are also transformed into these oxides by hydrolysis. By hydrolysis of 1.4-dichloro-diarsenane only a small amount of 1.4-epoxo-arsenane is formed, whereas mainly a dimer of this oxide results. Solvolysis of 2.6-dichloro-diarsa-[3.3.0]-bicyclooctane with water, hydrogen sulphide or methylamine leads to 7-oxa-, 7-thia- and 7-methylaza-2.5-diarsa-noradamantane, respectively.     

Quantitative goldbestimmung in filmmaterialien mittels flammenloser atomabsorption

A graphite rod electrothermal atomizer has been used for the AAS determination of traces of gold in hydrochloric and in hydrobromic acid solutions, and also after extraction into HBr-saturated methyl isobutyl ketone. Photographic film samples were decomposed first by enzyme action then by nitric acid/peroxide oxidation, and the gold was extracted into MIBK. For 10-μl aliquots of solution the 3s limits of detection were 3 × 10^?10g for aqueous solutions, 7 × 10^?10g for MIBK, and 7 × 10^?9 g/cm² for film.