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1.
The formation of complexes between tin(IV) and o-diphenols, and o-hydroxyquinones, has been studied spectrophotometrically. Simple o-hydroxyquinones do not react with tin(IV), chloranilic acid gives an SnR2 complex, and o-diphenols give SnR3 complexes. The reactions of tin(IV) with hydroxyxanthene dyes to give coloured products were considered for their possible analytical utility: the pH range, absorption spectrum, solubility and composition of the complexes were investigated, and the stability constants determined. Analytical procedures have been developed for tin and checked for precision and sensitivity: gallein and hydroxyhydroquinonephthalein (dihydroxyfluorescein) are to be recommended. 相似文献
2.
An n-octylmethyl, diphenyl-polysiloxane called SOP-50-Octyl was prepared by a condensation reaction of bis(dimethylamino) n-octylmethylsilane with diphenylsilanediol. The resulting copolymer was a gum with high molecular weight and was obtained with a yield of 80%. 1H and 29Si NMR spectroscopy revealed that the copolymer was a 52% octylmethyl, 48% diphenyl-polysiloxane with random microstructure. Small cyclic impurities could be almost quantitatively removed via a purification step. SOP-50-Octyl was used as stationary phase for the preparation of wall coated open tubular fused silica capillary columns for gas-liquid chromatography. The capillary columns exhibited high separation efficiency and high inertness. The stationary phase offered a unique selectivity due to its unique composition. The Rohrschneider-McReynolds constants indicated a low overall polarity in spite of the high phenyl content, as the polarity was distinctly decreased by the octyl substituent. Furthermore, the octyl substituent was responsible for a high column bleed, reducing the maximum allowable operating temperature to 280 degrees C. The elution temperatures of apolar compounds were increased due to increased interaction of the octyl substituent with the analytes. Some applications with volatile and semi-volatile organic compounds illustrate that SOP-50-Octyl is an excellent choice for confirmational analyses. 相似文献
3.
Daniel Bellu Hanspeter Fischer Hans Greuter Pierre Martin 《Helvetica chimica acta》1978,61(5):1784-1813
Syntheses of Moniliformin, a Mycotoxine with a Cyclobutenedione Structure Six different routes to 3-hydroxy-3-cyclobutene-1, 2-dione ( 4 ), the free acid of the mycotoxine Moniliformin (=alkali salt of 4 ) are described. A common feature of all pathways is the synthesis of cyclobutanes having the oxidation level 6. Moniliformin precursors which are easily transformed to 4 by acid catalysed hydrolysis include [2+2]-cycloadducts of ketene with tetraalkoxy-olefins, 3,4,4-trialkoxycyclobutenes, derivatives of polyfluorinated cyclobutenes, the brominated [2+2]-cycloadduct of ethyl vinyl ether and dichloroketene, tetrabromocyclobutanone, [2+2]-photocycloadducts of dichlorovinylenecarbonate with dichloroethylenes, and the dimer of chloroketene. The most convenient synthesis via the [2+2]-cycloadduct of tetraethoxyethylene and ketene ( 14b ) is reported in detail and produces 4 in four simple steps in 57% overall yield. In addition, two new syntheses of squaric acid ( 56 ) are described. 相似文献
4.
On the Reaction of Some 2H-Pyran-2-one Derivatives with Primary Amines The versatile reactivity of 6-unsubstituted 2H-pyran-2-ones towards aliphatic and aromatic amines has been studied. It was found that the result of the reaction depends not only on the substitution of 2H-pyran-2-ones and on the structure of amines, but also on the stoichiometric ratio of reacting compounds. 相似文献
5.
The FOGO method is used to calculate proton affinities and lithium cation affinities. The molecules of primary interest in this study are the methyl-substituted amines. In addition, the lithium cation affinity of HF, H2O, CH3OH, H2CO, and HCN are calculated for comparison. Geometries of all species are fully optimized with a double-zeta (DZ) basis set, including polarization on hydrogen and the first-row elements by floating orbitals. Comparison with experimental values demonstrates that structural data and proton affinities resulting from this type of ab initio calculation are of chemical accuracy. The lithium cation affinities are also reasonably well reproduced, but the small experimental differences are not within the accuracy, which can be expected from this type of calculation. 相似文献
6.
Hanspeter Huber 《Journal of Molecular Structure》1981,76(3):277-284
The floating orbital geometry optimization (FOGO) described previously is applied to H2O2, NH3, HNC, HNO, HNCO, and CH3OH. In the FOGO method we apply two analytically calculated energy gradients in a variable metric method. Some orbitals are no longer fixed on the corresponding nuclei, but their position is optimized simultaneously with the nuclear coordinates. It is shown that relative energies (e.g. rotational barriers) are obtained with similar accuracy to basis sets including polarization functions. Further, it is confirmed that FOGO yields excellent dipole moments. The FOGO method involves a considerable time saving compared to conventional calculations with DZ + P basis sets. 相似文献
7.
Pter Molnr Jzsef Deli Zoltn Matus Gyula Tth Andrea Steck Hanspeter Pfander 《Helvetica chimica acta》1997,80(1):221-229
β-Cryptoxanthin ( 1 ) was acetylated and then epoxidized with monoperoxyphthalic acid. After hydrolysis, repeated chromatography, and crystallization, (3S,5R,6S)-5,6-epoxy-β-cryptoxanthin ( 3 ), (3S,5S,6R)-5,6-epoxy-β-cryptoxanthin ( 4 ), (3R,5′R,6′R)-5′,6′-epoxy-β-cryptoxanthin ( 5 ), (3S,5R,6S,5′R,6′S)-5,6:5′,6′-diepoxy-β-cryp-toxanthin ( 6 ), and (3S,5S,6R,5′S,6′R)-5,6:5′,6′-diepoxy-β-cryptoxanthin ( 7 ) were isolated as main products and characterized by their UV/VIS, CD, 1H- and 13C-NMR, and mass spectra. The comparison of the carotenoid isolated from yellow, tomato-shaped paprika (Capsicum annuum var. lycopersiciforme flavum) with 3–5 strongly supports the structure of 3 for the natural product. 相似文献
8.
Using semiempirical and ab initio procedures, the most stable conformations of meso- and rac-bioxirane and of some substituted 1,2:3,4-diepoxides were calculated. For threo-diepoxides (having the same relative configurations as rac-bioxirane, 3 ), two stable conformations with CCCC dihedral angles of ca. 90 and ca. 270° were found. For erythro-diepoxides (derivatives of meso-bioxirane, 4 ) the calculations suggest three preferred conformations with corresponding dihedral CCCC angles of ca. 90°, ca. 180°, and ca. 270°. The calculations are in fair agreement with the experimental data available for the unsubstituted compounds 3 and 4 . 相似文献
9.
Novel Synthesis of (?)-(R)-Cembrene A, Synthesis of (+)-(R)-Cembrenene and (+)-(S)-Cembrene A novel synthesis of (?)-(R)-cembrene A ((?)- 3 ) was developed using the Sharpless epoxidation for the introduction of the chiral center. Furthermore, the synthesis of (+)-(R)-cembrenene ((+)- 4 ) showed that this cembranoid must have the (R)-configuration and not, as previously reported, the (S)-configuration. Selective hydrogenation of (+)- 4 afforded (+)-(S)-cenibrene ((+)- 5 ). 相似文献
10.
The nucleophilic attack of substituted anilines at position 6 of methyl coumalate (1) opens the α-pyrone ring to form 4-arylamino-3-(methoxycarbonyl)butadien-1-carboxylic acid 2 (Scheme 1). The latter are easily decarboxylated at room temperature in polar aprotic solvents to 1-arylamino-2-(methoxycarbonyl)butadiene 4 which smoothly undergo regio- and stereospecific Diels-Alder reactions with different dienophiles. 相似文献