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121.
The asymmetric 1,2-addition of trimethylsilyl cyanide to aldehyde SAMP-hydrazones in the presence of titanium tetrachloride and diethylether in dichloromethane at −100°C up to room temperature, removal of the chiral auxiliary and acid hydrolysis affords α-amino acids in high enantiomeric excesses (ee=94-97%). 相似文献
122.
Storsberg J Yao ML Ocal N de Meijere A Adam AE Kaufmann DE 《Chemical communications (Cambridge, England)》2005,(45):5665-5666
The first example of a pi,sigma domino-Heck reaction under concomitant rearrangement of the tetracyclic allylcyclopropane endo,exo-bishomobarrelene (5) is reported; the stereoselective reaction proceeds via an intramolecular insertion of a primarily-formed carbopalladation intermediate into a strained cyclopropane C-C sigma-bond, giving 9. 相似文献
123.
Synthesis, IR Spectrum, and Crystal Structure of N,N'-Bis(trimethylsilyl)benzamidinium Tetrachloroferrate(III) The title compound [C6H5? C(NHSiMe3)2][FeCl4] is obtained by the reaction of FeCl3 with N,N,N'-tris(trimethylsilyl)benzamidine in the presence of tetrahydrofurane, forming yellow, moisture sensitive crystals. The compound is characterized by its IR spectrum as well as by an X-ray structure determination. Space group P21/n, Z = 8, 5974 independent observed reflexions, R = 0.066. The lattice dimensions are at ?70°C: a = 2110.7, b = 1109.5, c = 2120.4 pm; β = 111.17º. The compound forms ion pairs, in which the H atoms of the amidinium cation are coordinated with one chlorine ligand of the FeCl4? ion in a chelating manner. 相似文献
124.
The phenolic oxidation of 2',4-dihydroxy-4'-methoxy-β-methylchalcone using alkaline potassium ferricyanide gives an aurone rather than an isoflavone. This result is discussed in the context of current theories regarding the biosynthesis of flavonoid and isoflavonoid compounds. 相似文献
125.
From a molecular orbital study of model systems we derive the electronic requirements for the Grob fragmentation. The necessary condition for an allowed fragmentation in an X-C1-C2-C3-N system, or the amino cation +C1-C2-C3-N is the level ordering A below S . This in turn is set by maximal through-bond coupling of the empty cation orbital and the nitrogen lone pair. The conformational dependence of through-bond coupling is exactly that derived by Grob, namely parallel orientation of the cation orbital (or the C-X bond), the C2-C3-σ-bond, and the N-lone-pair. When the C1-C2-C3 and C2-C3-N angles are small, the through-space interaction dominates, reversing the level ordering to S below A , and consequently makes the fragmentation forbidden even though the conformational requirements for it are met. Ring closure becomes allowed. Some examples exploiting this result are presented, as well as procedures for enhancing through-bond coupling and thus fragmentation. The through-bond-effect has also kinetic consequences, allowing the definition of a new type of remote neighbouring group participation operative through bonds and not by direct overlap. The position of equilibria in nitrogen inversion processes should also be influenced by remote substituents which are π-acceptors or donors. 相似文献
126.
Monochrome coloured glass beads of the Merovingians (5th–7th cent. AD) have been examined by different analytical methods. The elemental composition of a large number of mostly unprepared
beads have been measured non-destructively by X-ray fluorescence analysis. After subtracting the content of the colouring
oxides of the glass beads and normalising the residual values to 100% an identical soda-lime-glass matrix was obtained. X-ray
diffraction was used for the identification of the crystalline colouring and opacifying pigments (SnO2, Cu, Cu2O, PbSnO3), and scanning electron microscopy as well as electron probe microanalysis were applied to study the microstructure and the
composition of white, brown, green, orange and yellow coloured glass beads. Oxidised metals, alloys (lead, copper, bronze,
brass and mixtures of them) and iron smelting slag have been identified as raw materials to colour the soda-lime-glass. 相似文献
127.
Different synthetic routes for the preparation of diiodo(methylthio)gallane are given. Some reactions of this compound with Lewis bases, such as O(CH3)2, S(CH3)2, S2(CH3)2, N(CH3)3, P(CH3)3, and other compounds, such as CH3I, CH3OH, C2H5OH, C2H5SH, i-C3H7SH, and C2H5SeH are investigated. Spectra and some physical and chemical properties of the new compounds are reported. The structure of diiodo(methylthio)gallane is discussed in view of some interesting differences of this molecule in solution and in crystal form. 相似文献
128.
A high-performance liquid chromatographic procedure was developed for the isolation and quantitation of coumarin from vanilla-based liquid flavorings of Mexican origin. Forty products representing fourteen different Mexican brands were assayed for coumarin, vanillin, and ethyl vanillin by the proposed method. The procedure has been adapted to the analysis of other products including domestic vanilla extracts and imitation vanilla flavorings for vanillin, ethyl vanillin, 4-hydroxybenzaldehyde and piperonal. Chromatographic retention data for thirty-seven compounds associated with vanillin and vanilla products employing two mobile phase systems are presented. 相似文献
129.
Max Schmidt und Dieter Franz 《Fresenius' Journal of Analytical Chemistry》1965,215(5):395-400
Zusammenfassung Es wird ein Verfahren zur Bestimmung von Stibin beschrieben, das sich sowohl zur Analyse von SbH3 in organischen Lösungsmitteln als auch zur Bestimmung von flüssigem oder festem SbH3 eignet. Hierbei wird das Stibin mit überschüssigem Brom zu SbV oxydiert, danach mit SO2 zu SbIII reduziert und dieses oxydimetrisch mit Jod oder Bromat titriert.
Herrn Professor Dr. C. Mahr zum 65. Geburtstag gewidmet. 相似文献
Summary A method is proposed for the determination of stibine, applicable to its solutions in organic solvents and also to the solvent-free liquid or solid substance. The procedure involves oxidation of SbH3 with an excess of bromine to SbV, reduction to SbIII with SO2, and oxidimetric titration of the trivalent antimony with iodine or bromate.
Herrn Professor Dr. C. Mahr zum 65. Geburtstag gewidmet. 相似文献
130.
N-(2-Nitro)benzoylamino acids were prepared by 2-nitrobenzoylation of amino acids via the mixed ethylcarbonic anhydride procedure. They were reduced catalytically to N-(2-amino)benzoylamino acids which underwent cyclization to the corresponding lactams under a variety of conditions. The use of this reaction sequence for stepwise degradation of peptides seems possible. 相似文献