Synthesis and properties of azoles and their derivatives. 10. Synthesis of 3,5-diaryl-4-nitroisoxazoles

A method was proposed for the synthesis of 3,5-diaryl-4-nitroisoxazoles entailing the brominatian of potassium salts of the corresponding 3,5-diaryl-²-isoxazolinyl-4-nitronic acids. The method may be used for the conversions of both the trans and cis isomers of 3,5-disubstituted 4-nitro-²-isoxazolines.Communication 9, See [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 189–192, February, 1985.     

Loss of isocyanic acid from the internal oxadiazole ring of protonated molecules of some 2,5-diaryl-1,3,4-oxadiazoles

The fragmentation pattern of some protonated 2,5-diaryl-1,3,4-oxadiazoles is discussed. An unusual decomposition consisting of elimination of the isocyanic acid molecule from the internal oxadiazole ring was found. This fragmentation pathway was deduced on the basis of B/E linked scan mass spectra of metastable ions with liquid secondary ion mass spectrometry as the ionization method and also of low-energy CID mass spectra where electrospray was used as the ionization technique. High resolution measurements were also performed.     

Pyrolysis of propane in the presence of acetylene

Pyrolysis of propane in the presence of acetylene and acetylene labeled with C-14 has been studied in the temperature range of 833–1019 K. The inhibition effect of acetylene on the thermal decomposition of propane is turning into an accelerating effect at higher temperature.

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C¹⁴ 833–1019 . .

     

Flotation—spectrophotometric determination of osmium with thiocyanate and methylene blue

A sensitive flotation—spectrophotometric method, based on the ion associate formed by the anionic thiocyanate complex of osmium with the basic dye methylene blue (MB) is described. The ion associate precipitates when the aqueous solution is shaken with toluene, and the separated and washed compound is dissolved in acetone. The molar absorptivity is 2.2 × 10⁵ l mol^-1 cm^-1 at 655 nm. Beer's law is obeyed. The molar ratio of Os:SCN:MB in the separated and washed ion associate is 1:6:3. Ruthenium reacts similarly. The method is applied to the determination of traces of osmium in crucible platinum after separation of osmium by distillation as tetroxide.     

NAA as viewed from the perspective of international atomic energy agency intercomparison tests

Results of several IAEA intercomparison runs organized over the last 8 years are analyzed from the point of view of contribution and performance of NAA as compared to other techniques. It is shown that NAA is the method of good accuracy and precision providing on average greater share of results than any other single analytical technique. The prominent position of NAA among other methods used in trace analyses seems to be firmly established and there are no signs that there might be any change of the trend in the nearest future.     

Facile synthesis of acyclic azanucleosides from N-pivaloyloxymethyl amides and sulfonamides: synthesis of aza-analogues of Ganciclovir

N-Pivaloyloxymethyl amides and sulfonamides, readily available from N-alkylation of both amides and sulfonamides with commercial chloromethyl pivaloate, were converted into acyclic azanucleosides via a one-pot base silylation/nucleoside coupling procedure.     

Synthesis, structure and properties of N-acetylated derivatives of methyl 5-amino-1H-[1,2,4]triazole-3-carboxylate

Methyl 5-amino-1H-[1,2,4]triazole-3-carboxylate hydrochloride (1). and free ester (2). were obtained and 2 was reacted with Ac(2)O to give the acetylated products 3-6. Compounds 1-6 were studied using HPLC, GC-MS, FTIR and multinuclear NMR spectroscopy, including the cross-polarisation magic angle spinning (CPMAS) technique. The results of the acetylation of 2 were compared to those of the acetylation of 5-amino-1H-[1,2,4]triazole, and for 2 a significant decrease in the susceptibility to acetylation was found. The reaction of 2 with Ac(2)O at 20 degrees C, regardless of the amount and the concentration of the latter, including neat Ac(2)O, proceeds fully regioselectively and leads to one product: methyl 1-acetyl-5-amino-1H-[1,2,4]triazole-3-carboxylate (3). In sharp contrast to 5-amino-1H-[1,2,4]triazole, neither an additional monoacetylated isomer, whether annular or exocyclic, nor any diacetylated derivative could be detected. The diacetylation of 2 requires the process to be carried out in neat boiling Ac(2)O and, as in the case of 5-amino-1H-[1,2,4]triazole, gives two diacetylated isomers. These are methyl 1-acetyl-3-(acetylamino)-1H-[1,2,4]triazole-5-carboxylate (4) and 1-acetyl-5-(acetylamino)-1H-[1,2,4]triazole-3-carboxylate (5). Hypothetical pathways of their formation have been suggested. A mixture of 4 and 5 upon hydrolysis of the ring acetyl group gives the monoacetylated derivative methyl 5-(acetylamino)-1H-[1,2,4]triazole-3-carboxylate (6). The spectroscopic, structural and conformational characteristics of compounds 1-6 have been given and methods for their preparation have been provided.     

Solvent extraction and bulk liquid membrane transport of Co(II) and Ni(II) ammine cations by proton-ionizable crown ethers

Separation efficiencies and selectivities in solvent extraction of Co(II) and Ni(H) ammine cations from aqueous solutions into chloroform and toluene and in transport through bulk toluene membranes by proton-ionizable crown ethers have been determined. Six proton-ionizable crown ethers with differing lipophilicities, polyether cavity sizes and ionizable groups (carboxylic and sulfonic acid functions) were examined. Higher selectivity and efficiency for Co(II) ammine cation extraction was observed for the more lipophilic, proton-ionizable crown ethers. Highly lipophilic crown carboxylic acids provided effective and selective transport of Co(II) ammine cations through bulk toluene membranes.Presented in part at the 6th International Symposium on High Purity Materials in Science and Technology: Preparation, Characterization and Application of Well-Defined Materials, Dresden, GDR, May 1985, Poster D91, Poster Abstracts, pp. 144, 145.All extraction and transport experiments were conducted at this location.     

Spectrophotometric determination of Fe(II) in milligram solid samples

The analytical procedure of determination of Fe(II) in the presence of Fe(III) in milligram samples is proposed. A solid sample is dissolved in hydrochloric acid in argon atmosphere. Subsequently, the pH-value of the solution is fixed and Fe(III) complexed by phosphoric buffer. At the next step Fe(II) is oxidized by -molybdosilicic acid. Finally, the intensity of colouring caused by the reduced form of the acid is measured at the wavelength 770 nm. The proper treatment of the sample during oxidation, and immediately before, is decisive for the accuracy of the analysis. The method was verified by means of the analysis of synthetic magnetite. The theoretical content of Fe(II) was 24.12%, the determined one was 24.02 ± 0.10%. The method was applied to the determination of the homogeneity of an iron catalyst for ammonia synthesis.     

Hilbert functions and Betti numbers in a flat family

Summary This paper is dedicated to the study of Hilbert functions and Betti numbers of the projective varieties in a flat family. We prove that the Hilbert function H(X _y ,n),y Y-a parameter scheme-is lower semicontinuous for any fixed n. In case Y is integral and noetherian we obtain the well-known fact that the set V Y where H(X _y ,n)is maximal for all n's is open and nonempty. We show also that b_i(X _y )-the i- th Betti number of X_y—is upper semicontinuous for y V. The paper contains also a number of results concerning the relations among the various Betti numbers.Member of G.N.S.A.G.A.-C.N.R. Supported in part by M.P.I. (Italian Minstry of Education).