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61.
Indole lactones 8 and 14 were synthesized as a means of functionalizing the 1-isopropyl substituent of the indole nucleus. Lactone 8 , upon reduction with diisobutylaluminum hydride, produces lactol 9 which behaves like a masked hydroxy aldehyde and undergoes a Horner-Emmons reaction with triethyl phosphonoacteate to give α,β-unsaturated ester 3 which possesses a hydroxyl group on the 1-isopropyl moiety. 相似文献
62.
Gert Brandl Fritz Kastner Rainer Fritsch Herbert Zinner Albrecht Mannschreck 《Monatshefte für Chemie / Chemical Monthly》1992,123(11):1059-1069
Summary A procedure is described which serves to measure circular dichrograms () on line during stops of flow in liquid chromatography. Since the concentration of substrate in the spectrometer cell during the stop is not known, the differential absorption coefficients are calculated from the experimental differential absorbances A by means of UV absorption (i. e. photomultiplier voltage) data. Verifications of the procedure are obtained by its application to three substrates (Table 1), the () spectra of which were known. The present on-line technique is compared with a corresponding off-line method.The N,N-dimethylthiobenzamides1 and2 as well as the 9,10-phenanthrenequinone7 consist of interconvertible enantiomers because their planar states are destabilized by steric overcrowding of groups. The unknown dichrograms () of1, 2 and7 are obtained (Figs. 2 and 4) and discussed with reference to the helicities of these molecules.In memory of the late Professor Dr. Dr. h. c. Günther Snatzke. 相似文献
63.
Huttenloch O Laxman E Waldmann H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(20):4767-4780
The development of a method for the optimization of chiral ligands for the steric steering of enantioselective Cu-catalyzed conjugate additions of Znalkyls to enones is described. The method is based on combinatorial principles and solid-phase techniques. It includes the combinatorial synthesis of chiral bispidine-derived ligands embodying a phosphoramidite group on the solid phase and their investigation in immobilized form in the conjugate addition of ZnEt2 to cyclohexenone as test reaction. The best identified ligands were also synthesized separately and investigated in its soluble form. The results obtained for the polymer-bound ligands correctly mirrored the performance of the soluble ligands. The library embodied members giving ee values varying between 3 and 67%. The "positional scanning" approach proved to be invalid for the study of the ligand system, indicating that this approach in general should be applied with care. Taken together, the method allowed for rapid and efficient optimization of the ligands and led to the development of the first enantioselective, Cu-catalyzed conjugate addition reaction with a polymer-bound ligand. 相似文献
64.
S. Korhammer Rolf Herzig Peter Schramel Jorma Kumpulainen Bernd Markert Herbert Muntau Philippe Quevauviller 《Accreditation and quality assurance》2000,5(6):238-242
Cabbage is frequently used in environmental monitoring and food control, and, hence, cabbage reference materials (RMs) are
required for ensuring quality assurance. A cabbage RM was prepared in view of certification of specific elements from the
"black list" of high toxicological interest and nutritive importance. All tasks of the RM production (production of the plant
material, cutting and freeze-drying, determination of the residual water content, preparation of the RM, homogeneity testing,
stability testing, certification measurements) are described in detail.
Received: 12 November 1999 / Accepted: 29 January 2000 相似文献
65.
Vibrational spectroscopy is uniquely capable of determining the structure and dynamics arising from the rotational degrees of freedom in molecular solids. Vibrational spectroscopy is sensitive to phenomena occurring on a time scale between the slow scale of magnetic, resonance methods and fast scale of diffraction methods; a time scale appropriate for both internal and overall rotation. Rotational motion of molecules in crystals provide examples of very simple reactions. Our understanding of the spectra of reacting molecules can thus be tested on these systems, and we conclude that Redfield equations can describe such spectra.A rich variety of motional effects are described: (1) The libration of the water of hydration in sodium perchlorate which illustrates a simple reacting system. (2) The libration of the adamantane molecule in both its ordered and disordered crystal phases which illustrates intermolecular interactions in organic crystals and the consequences of disorder. (3) The libration of the ammonium ion in crystals of ammonium salts which illustrated both change of orientational position by tunneling and the subtle orientating effects of isotopic substitution. (4) The internal rotation in n-alkane crystals which illustrates the ability to determine conformers and the relationship between the occurrence of disordered conformers and the occurrence of phase transitions. 相似文献
66.
Laser flash photolysis and stopped-flow methods have been employed to determine the kinetics of the reactions of benzhydrylium ions with both termini of the thiocyanate ion. In contrast to previous investigations which reported sulfur/nitrogen ratios of k(S)/k(N) = 2-10 for the reactions of carbocations with SCN(-), values of k(S)/k(N) = 10(3)-10(4) are now derived from absolute rate constants. This discrepancy is explained by the fact that the data determined in this investigation are the first which refer to activation-controlled attack of carbocations at both termini of the thiocyanate ion, while previous reactivity ratios included diffusion-controlled reactions. It is concluded that the selectivities of the reactions of carbocations with the thiocyanate ion cannot be explained by the hard soft acid base principle. 相似文献
67.
Allenyl cations, generated from allenyl or alkynyl halides and Ag+, attack styrene at the side chain or at the aromatic nucleus. The allenyl/alkynyl product ratio is dependent on the structure of the precursor halide except for highly substituted systems. 相似文献
68.
Siebert HC Born K André S Frank M Kaltner H von der Lieth CW Heck AJ Jiménez-Barbero J Kopitz J Gabius HJ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,12(2):388-402
The branched pentasaccharide chain of ganglioside GM1 is a prominent cell surface ligand, for example, for cholera toxin or tumor growth-regulatory homodimeric galectins. This activity profile via protein recognition prompted us to examine the binding properties of peptides with this specificity. Our study provides insights into the mechanism of molecular interaction of this thus far unexplored size limit of the protein part. We used three pentadecapeptides in a combined approach of mass spectrometry, NMR spectroscopy and molecular modelling to analyze the ligand binding in solution. Availability of charged and hydrophobic functionalities affected the intramolecular flexibility of the peptides differently. Backfolding led to restrictions in two cases; the flexibility was not reduced significantly by association of the ligand in its energetically privileged conformations. Major contributions to the interaction energy arise from the sialic acid moiety contacting Arg/Lys residues and the N-terminal charge. Considerable involvement of stacking between the monovalent ligand and aromatic rings could not be detected. This carbohydrate binding strategy is similar to how an adenoviral fiber knob targets sialylated glycans. Rational manipulation for an affinity enhancement can now be directed to reduce the flexibility, exploit the potential for stacking and acquire the cross-linking capacity of the natural lectins by peptide attachment to a suitable scaffold. 相似文献
69.
Stevan W. Djuri Richard B. Herbert Frederick G. Holliman 《Journal of heterocyclic chemistry》1985,22(5):1425-1428
A novel procedure for the chemoselective reduction of 2-acyl-1H-indole-3-carboxaldehydes has been developed. Low temperature lithium triethylborohydride reduction affords the indol-2-yl carbinol whilst sodium cyanoborohydride reduction in acetic acid affords the 3-hydroxymethyl analogs. Both processes are high yield, and provide access to intermediates of potential utility for indole alkaloid synthesis. 相似文献
70.
In catalytic end-point detection, the first drop of titrant in excess is not used for a stoichiometric reaction with the indicator (as in conventional titrations) but acts as, or liberates, a catalyst for the indicator reaction. A very small excess of titrant thus suffices to catalyze large amounts of the indicator reaction mixture. Such catalytic end-points are therefore very sensitive. Terminology is discussed briefly. The various types of titration (direct, with a “brake”, reversed, indirect and substitution) and of end-point detection (visual, olfactory, photometric, thermometric and electrometric) are described. Applications of these techniques are summarized. 相似文献