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31.
Steric factors have been shown to be responsible for the anomalous dehydration of 2-phenylindole-3-carboxamide (1) to 2-phenylindole-3-carbonitrile (3) by lithium aluminum hydride. This steric effect was also reflected in the reactions of 2-phenylindole (4) and its derivatives.
Anomale Dehydratisierung von 2-Phenylindol-3-carbonsäureamid zu 2-Phenyl-indol-3-carbonitril mit Lithiumaluminiumhydrid (Kurze Mitteilung)
Zusammenfassung Es wird gezeigt, daß für die anomale Dehydratisierung von 2-Phenylindol-3-carbonsäureamid (1) zum entsprechenden Nitril3 durch Lithiumaluminiumhydrid sterische Faktoren verantwortlich sind. Dieser sterische Effekt zeigt sich auch bei Reaktionen von 2-Phenylindol (4) und seiner Derivate.相似文献
32.
33.
S.A.Vieira Filho L.P. Duarte G.D.F. Silva O.W. Howarth I.S. Lula 《Helvetica chimica acta》2003,86(10):3445-3449
3β‐(Stearyloxy)olean‐12‐ene was isolated from a hexane extract of Austroplenckia populnea Reiss (Celastraceae) leaves. The structure was solved by means of quantitative 13C‐NMR, HMBC, HMQC, COSY, NOESY, and NOE difference spectra. The mass spectrum showed an [M+1]+ ion peak at m/z 693, and the molecular formula C48H84O2 was confirmed by combustion analysis. 相似文献
34.
Raymond J. Abraham Lee Griffiths Philip Loftus 《Journal of computational chemistry》1982,3(3):407-416
Alternative methods of estimating atomic charges in haloalkanes are presented, derived from quantum mechanical and classical treatments. A scheme based on a breakdown of the transmission of charge by polar atoms into one-bond, two-bond, and three-bond additive contributions is given, in which the one-bond effect is proportional to the difference in the electronegativities of the bonded atoms, and the two- and three-bond effects functions of the atomic electronegativity and polarizability. Suitable developments of the basic scheme, including an iterative self-consistent process, give calculated dipole moments for a variety of haloalkanes in good agreement with the observed values. The atomic charges obtained by this scheme are compared with other estimates of these charges. They are similar to those derived from a simple LCAO –MO scheme but differ from those obtained by population analysis of more refined quantum mechanical calculations. 相似文献
35.
M. Costa-Ferreira A. Dias C. Maximo M. J. Morgado G. Sena-Martins J. Cardoso Duarte 《Applied biochemistry and biotechnology》1994,44(3):231-242
Production of xylanolytic enzymes by anAspergillus niger CCMI 850 isolate was investigated in batch cultures. The effect of the composition of a fermentation medium that did not
include chemical inducers, on β-xylanase, β-xylosidase, α-l-arabinofuranosidase, and total cellulase activity was studied. With 4% xylan as the carbon source, about 65 U/mL of β-xylanase
was obtained, whereas the total cellulase activity was undetectable, under the specified conditions. This β-xylanase activity
represents the highest reported for a wild-type strain ofA. niger. The effect of pH and temperature on the activity of β-xylanase was studied. Partial characterization of the β-xylanase showed
that with insoluble birchwood as substrate theK
m
andV
max were 0.3 mM and 19 μmol/min, respectively. Aspects of using the crude β-xylanase preparation for applications in the pulp and paper industry
were discussed. 相似文献
36.
Cabeza A Ouyang X Sharma CV Aranda MA Bruque S Clearfield A 《Inorganic chemistry》2002,41(9):2325-2333
Nitrilotris(methylenephosphonic acid) (NTP, [N(CH(2)PO(3)H(2))(3)]) recently has been found to form three-dimensional porous structures with encapsulation of templates as well as layered and linear structures with template intercalation. It was, therefore, of interest to examine the type of organic-inorganic hybrids that would form with metal cations. Mn(II) was found to replace two of the six acid protons, while a third proton bonds to the nitrilo nitrogen, forming a zwitter ion. Two types of compounds were obtained. When the ratio of acid to Mn(II) was less than 10, a trihydrate, Mn[HN(CH(2)PO(3)H)(3)(H(2)O)(3)] (2) formed. Compound 2 is monoclinic P2(1)/c, with a = 9.283(2) A, b = 16.027(3) A, c = 9.7742(2) A, beta = 115.209(3) degrees, V = 1315.0(5) A(3), and Z = 4. The Mn atoms form zigzag chains bridged by two of the three phosphonate groups. The third phosphonate group is only involved in hydrogen bonding. The metal atoms are octahedrally coordinated with three of the sites occupied by water molecules. Adjacent chains are hydrogen-bonded to each other through POH and HN donors, and the additional participation of all the water hydrogens in H-bonding results in a corrugated sheet-like structure. Use of excess NTP at a ratio to metal of 10 to 1 yields an anhydrous compound Mn[HN(CH(2)PO(3)H)(3)] (1), P2(1)/n, a = 9.129(1) A, b = 8.408(1) A, c = 13.453(1) A, beta = 97.830(2) degrees, V = 1023.0(2) A(3), and Z = 4. Manganese is five coordinate forming a distorted square pyramid with oxygens from five different phosphonate groups. The sixth oxygen is 2.85 A from an adjacent Mn, preventing octahedral coordination. All the protonated atoms, three phosphonate oxygens and N, form moderately strong hydrogen bonds in a compact three-dimensional structure. The open-structured trihydrate forms a series of isostructural compounds with other divalent transition metal ions as well as with mixed-metal compositions. This is indicative that the hydrogen bonding controls the type of structure formed irrespective of the cation. 相似文献
37.
The 13C and proton NMR spectra of six porphyrins bearing the substituent orientation characteristic of the natural “Type-IX” arrangement are reported and assigned. Significant concentration effects in the spectra of the free base porphyrins, together with the broadening of the Cα (and occasionally Cβ) carbon resonances due to NH tautomerism caused a significant loss of data in these spectra. However, the spectra of the corresponding zinc(II) porphyrins (with addition of excess pyrrolidine) show that both these extraneous effects are completely removed to give well-resolved spectra with accurately reproducible chemical shifts. These spectra are assigned and an analysis of the chemical shifts allows the deduction of substituent chemical shift (SCS) parameters for the peripheral substituents at the beta and meso carbons. There is no global effect of these beta substituents, the beta carbon SCS being confined to the immediate pyrrole ring, and the meso carbon SCS to the two adjacent pyrrole rings. The SCS parameters are analyzed and it is shown how they can be used to predict the peripheral and meso carbon chemical shifts of any porphyrin bearing the substituents discussed. 相似文献
38.
Berman Abraham Shaked-Monderer Naomi 《Central European Journal of Operations Research》2022,30(3):1093-1099
Central European Journal of Operations Research - Completely positive matrices are matrices that can be decomposed as $$BB^T$$ , where B is an entrywise nonnegative matrix. These matrices have many... 相似文献
39.
R. S. Brusa M. Duarte Naia D. Margoni A. Zecca 《Applied Physics A: Materials Science & Processing》1995,60(5):447-453
We have determined the positron mobility (+) in polyethylene samples (67.2% crystalline, glass transition temperatureT
g=151 K) in the 64–400 K temperature range by Doppler shift measurements. A method based on the simulataneous observation of two lines from133Ba and137Cs radioactive sources together with the positron annihilation line, was employed to measure the Doppler shift of the 511 keV line as a function of the electric field applied to the samples. With this method we were able to measure at the same time the drift velocity of positrons and theS parameter. This parameter is very important in the interpretation of the mobility trend in samples where the positron states change with temperature. The positron mobility was corrected for positronium formation. + at 64 K is 31.7±0.8 cm2 V–1 s–1 then decreases up to 123 K, increases at 148 K and decreases again up to 170 K (+=26.9±0.8 cm2 V–s–). This sharp change in mobility is centred around the glass transition temperature of our samples. Then the mobility remains almost constant up to 230 K. From 250 K to 377 K, + increases and reaches the value of 38.4±1.0 cm2 V–1s–1. The corrected experimental data were well fitted by a simple model taking into account scattering and a thermally activated process (hopping mechanism). 相似文献
40.