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1.
2.
G. Gargaro F. Gasparrini D. Misiti G. Palmieri M. Pierini C. Villani 《Chromatographia》1987,24(1):505-509
Summary Enantiomers of several sulfoxides and some selenoxides can be easily separated by using a new chiral stationary phase (CSP-DACH-DNB)
containing the 3,5-dinitrobenzoyl derivative of R,R-(-)1,2-diamino-cyclohexane as selector, covalently bonded to the siliceous
matrix. The easy operative conditions and the high enantioselectivity values (α) allow a direct transfer of the analytical
separations to a semi-preparative and preparative scale. 相似文献
3.
A. B. Pierini G. L. Borosky M. T. Baumgartner 《International journal of quantum chemistry》1992,41(5):759-761
We here report an AM 1 study for the reaction of different types of radicals with the acetone enolate ion 1 and other ambident nucleophiles. The theoretical reactivity order determined is phenyl > methyl > tert-butyl ? bicyclo-[2.2.1]hept-1-yl. The activation energy for the coupling of aliphatic radicals is ascribed mainly to nonbonded interactions. Considering possible solvent effects, we propose the same order of reactivity in solution. The coupling reaction of phenyl radical with 1 is an exothermic process with nonactivation energy in the gas phase. Any energy barrier in solution is here ascribed to desolvation of the anion. The regiochemistry of the coupling of radicals with ambident nucleophiles such as 1 , phenoxide, or phenylamide anions is also explained on a theoretical basis. © 1992 John Wiley & Sons, Inc. 相似文献
4.
The face selectivity (endo-face vs. exo-face attack onto the exocyclic s-cis-butadiene moiety) of the [4+2]cycloadditions of 5,6-bis((D)methylidene)-2-bicyclo-[2.2.2]octene ( 11 ) to strong dienophiles has been determined in benzene at 25°. It is ca. 95/5, 75/5, 70/30, 60/40 and 50/50 for N-phenyltriazolinedione (NPTAD), tetracyanoethylene (TCE), dimethyl acetylenedicarboxylate (DMAD), maleic anhydride (MA) and singlet oxygen (1O2), respectively. The endo-face preference is probably due to a participation of the homoconjugated double bond at C(2), C(3) which makes the etheno bridge more polarizable than the ethano bridge in 11. The absence of face selectivity with 1O2 is consistent with an entropy-controlled mechanism involving the intermediacy of an exciplex. 相似文献
5.
6.
Prof. Tiziana Benincori Dr. Valentina Bonometti Dr. Roberto Cirilli Prof. Patrizia R. Mussini Dr. Andrea Marchesi Prof. Marco Pierini Dr. Tullio Pilati Dr. Simona Rizzo Prof. Francesco Sannicolò 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(1):165-181
A series of tris‐aryl phosphane oxides existing as residual enantiomers or diastereoisomers with substituents on the aryl rings differing in size and electronic properties were synthesized and characterized. Their electronic properties were evaluated on the basis of their electrochemical oxidation and reduction potentials together with those of the corresponding “blade bromides” (i.e., the naphthalene derivatives displaying the same substitution pattern of the tris‐naphthyl phosphane oxide blades, with a bromo substituent where the phosphorus atom is located) determined by CV. The residual stereoisomeric phosphane oxides were isolated in a stereochemically pure state and were found to be highly configurationally stable at room temperature (stereoisomerization barriers of about 27 kcal mol?1). The chiroptical properties of the residual stereoisomers and the assignments of absolute configuration are discussed. The configurational stability of residual tris‐aryl phosphane oxides was found to be scarcely influenced by the electronic properties of the substituents present on the aromatic rings constituting the blades, while steric effects play the most relevant role. Detailed theoretical calculations are in agreement with the experimental results and also contribute to a rational interpretation of the stereodynamics of these systems. 相似文献
7.
DellErba C Gasparrini F Grilli S Lunazzi L Mazzanti A Novi M Pierini M Tavani C Villani C 《The Journal of organic chemistry》2002,67(5):1663-1668
Static and dynamic stereochemistry of the hydrocarbon comprising a phenyl ring bearing two alpha-naphthyl substituents in the ortho positions, i.e., 1,2-di-(4-methyl-naphth-1-yl)-benzene 1, has been studied by a combination of variable temperature NMR, cryogenic HPLC, and MM calculations. Whereas in solution both syn (meso) and anti (chiral) forms were observed and the corresponding interconversion barrier was determined (Delta G(++) = 19.5 kcal mol(-1)), only the diastereoisomer anti was found to be present in the crystalline state (X-ray diffraction). When the molecule is rendered asymmetric by introduction of a nitro group in the phenyl ring as in 1,2-di-(4-methyl-naphth-1-yl)-4-nitrobenzene 2, the chiral syn and anti diastereoisomers are simultaneously present both in solution and in the solid state, albeit in different proportions. Cryogenic chromatography on a HPLC chiral stationary phase at 20 degrees C allowed the stereolabile diastereoisomers and the corresponding enantiomers to be separated. 相似文献
8.
Summary A dualsorbent trap containing graphitized carbon blacks was used for the collection of volatile and semi-volatile organic
pollutants from the atmosphere of different workplaces and from an above-ground parking lot. The method proved to be sensitive,
simple and reliable.
Thermal desorption and solvent extraction methods followed by GC-MS analysis were employed. 相似文献
9.
Summary A new graphitized carbon black, Carbograph 4, with a specific surface area of 240 m2 g−1 was studied in terms of enthalpy, entropy and free energy of adsorption, determined by gas chromatographic method on a series
of alkanes (C2−C6) and on benzene. The changes in the isosteric heat and entropy of adsorption when a non-polar stationary phase (squalane)
was added to the adsorbent were also investigated. The data obtained are discussed and compared to those present in the literature
for other graphitized carbon blacks. Some examples of separations obtained with Carbograph 4 are reported. 相似文献
10.
Summary In this paper we show that for a large class of steady solutions of the two-dimensional Euler equation and of the equation
of conservation of potential vorticity for equivalent-barotropic flows, instabilities can grow only if their energy concentrates
at length scales larger than that of the steady state. This possible growth of energy at large scales is accompanied by a
corresponding growth of enstrophy at small scales. Such a distribution of energy and enstrophy, which is well known in the
different context of two-dimensional turbulence, is therefore found to constitute a necessary mechanism for instability.
Riassunto In questo lavoro mostriamo che, per una vasta classe di soluzioni stazionarie dell'equazione di Eulero bidimensionale e dell'equazione della conservazione della vorticità potenziale per flussi quasi geostrofici, le instabilità possono crescere solo se la loro energia si concentra a scale con lunghezza caratteristica piú grande di quella della soluzione stazionaria. Questa possibile crescita di energia a grande scale è accompagnata da una corrispondente crescita di enstrofia a piccola scala. Tale distribuzione di energia ed entrofia, ben nota in turbolenza bidimensionale, si dimostra essere un meccanismo necessario per l'instabilità.
Резюме В этой работе мы показываем, что для большого класса стационарных решений двумерного уравнения Эйлера и уравнения сохранения потенциальной завихренности для эквивалентных баротропных потоков неустойчивости могут возрастатъ толъко в том случае, если их энергия концентрируется на масштабах с длинами, много большими, чем характерные длины стационарного состояния. Это возможное увеличение энергии на больших масштабах сопровождается соответствующим ростом ?энстрофии? на малых масштабах. Следовательно, указанное распределение энергии и ?энстрофии?, хорошо известное в двумерной турбулентости, представляет необходимый механизм для неустойчивости.相似文献