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21.
Isobutane and methane chemical ionization (CI) mass spectra of C-17a-epimeric, 17a-substituted 3-methoxyestra-1,3,5(10),8-tetraen-17a-ols and at C-17-epimeric 17-substituted 3-methoxyestra-1,3,5(10)-trien-17-ols, as well as of some their derivatives, have been studied. In each epimeric pair, the peak intensity ratio [MH-H(2)O](+) / [MH](+) is greater for stereoisomers having an axial (or quasi-axial) hydroxyl group. The same regularity in the peak intensity ratio [MH-CH(3)COOH](+) / [MH](+) is valid for acetates in the D-homo series. The observed quantitative differences in CI mass spectra of epimers are explained by steric hindrance of the attack of the proton-donating cation caused by the angular 18-methyl group. No differences in the ease of elimination of the silanol molecule were observed in CI mass spectra of epimeric silyl ethers. 相似文献
22.
23.
Roman F. Nalewajski Sebastito J. Formosinho Ant
nio J.C. Varandas Janusz Mrozek 《International journal of quantum chemistry》1994,52(5):1153-1176
The recently introduced set of the quadratic, two-electron covalent and ionic valence indices is used to investigate the bond-breaking–bond-forming (BB-BF ) process in an atom exchange reaction between H2 and X (X = H, F—I) as well as in the O2—H system. Valence changes accompanying selected charge reorganizations are examined within the three-orbital model and valence diagrams for symmetric transition states (TS s) are given. The UHF valence data for Li2O and CO2 and the H—H—X, O—O—H, and O—H—O (ABC) TS s (collinear and angular) are reported and compared to valence data in the separated fragments limits (SFL ), AB and BC. The overall valence, ν(ABC), and the total (ionic plus covalent) diatomic valences, νAB and νBC, are used as measures of the overall bond-order in a concerted BB–BF reaction, to test the postulate of the bond-energy–bond-order (BEBO ) model. In collinear TS s of H2X, ν ? ?1, i.e., one bonding electron pari, is found to be roughly preserved, whereas in the angular H2X and in collinear O—H—O TS s, the effect of increased valence at the saddle-point is observed, relative to that of diatomic fragments (reactiants or products). For the angular O—O—H TS , a similar increase in | ν (ABC)| relative to both O2 and OH SFL s is detected; smaller changes relative to the O2 data are found in the collinear TS . This observation is in agreement with earlier predictions from the intersecting-state model. The relative diatomic valences, ν/ν and ν/ν, are shown to conserve the overall relative bond multiplicity around 1 in both collinear and angular TS s of the H2—X systems. © 1994 John Wiley & Sons, Inc. 相似文献
24.
The modified ionic and covalent valence indices are introduced, defined in the framework of the two-particle density matrix, with respect to the reference state of separated atoms or ions (SAL ). They include only quadratic contributions in changes of the molecular charge-and-bond order matrix elements, relative to the SAL . General properties of the modified valence indices are examined and illustrative qualitative results for model systems are presented. Numerical UHF SCF MO valence data for selected diatomic and triatomic molecules are reported and interpreted in terms of the valence saturation effect and the ionic vs. covalent valence competition. A three-orbital valence model of a symmetric transition state of the bond-forming–bond-breaking reaction supports the BEBO model postulate of preservation of the total “bond order.” The model predictions are compared with the UHF numerical values. © 1994 John Wiley & Sons, Inc. 相似文献
25.
[formula: see text] The reaction of secondary and primary alcohols with highly fluorinated 3,4,5-tris(5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafluorododecan- 1-yloxy)benzoic acid in the presence of Ph3P and DIAD in THF at room temperature (fluorous Mitsunobu) resulted in a simple, chromatography-free isolation protocol with excellent yields (83-96%). 相似文献
26.
Piotr Kutrowski Dominika Sukowska Renata Pytlowany Roman Dziembaj 《Reaction Kinetics and Catalysis Letters》2004,81(1):3-11
Catalytic performance of Ba(OH)2 and Sr(OH)2 in self-condensation of acetone was examined in the temperature range from 273 to 303 K. A kinetic model of second order with respect to acetone was used for interpretation of the results obtained for the diacetone alcohol formation.This revised version was published online in December 2005 with corrections to the Cover Date. 相似文献
27.
28.
Roman B?aszczyk 《Tetrahedron letters》2007,48(33):5859-5863
An efficient, diastereoselective synthesis of 5-substituted (2-thioxo-imidazolidin-4-yl)phosphonic acid diethyl esters from metallated diethyl isothiocyanatomethylphosphonate and activated imines has been developed. The three-step transformation of imidazolidine-2-thione derivatives into 1,2-diaminoalkylphosphonic acids is also described. 相似文献
29.
Cosper MM Jameson GN Davydov R Eidsness MK Hoffman BM Huynh BH Johnson MK 《Journal of the American Chemical Society》2002,124(47):14006-14007
The combination of resonance Raman, electron paramagnetic resonance and M?ssbauer spectroscopies has been used to investigate the effect of S-adenosyl-l-methionine (SAM) on the spectroscopic properties of the [4Fe-4S]2+ cluster in biotin synthase. The results indicate that SAM interacts directly at a unique iron site of the [4Fe-4S]2+ cluster in BioB and support the hypothesis of a common inner-sphere mechanism for the reductive cleavage of SAM in the radical SAM family of Fe-S enzymes. 相似文献
30.
Roman E. Sioda 《Monatshefte für Chemie / Chemical Monthly》1985,116(1):49-52
The specific dissolution rate, expressed in mol cm–2s–1, and time-variation of the rest potential of copper foil in an aerated aqueous solution ofpH = 2.0 were measured.
Die Auflösbarkeit von Kupfer-Folie in wäriger Lösung von pH 2 (Kurze Mitteilung)
Zusammenfassung Es wurde die spezifische Auflösungsgeschwindigkeit (in mol cm–2s–1) und die zeitliche Veränderung des Restpotentials von Kupfer-Folie in einer belüfteten wäßrigen Lösung von pH 2,0 gemessen.相似文献