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排序方式: 共有46条查询结果,搜索用时 15 毫秒
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M. Di Serio B. Apicella G. Grieco P. Iengo L. Fiocca R. Po E. Santacesaria 《Journal of molecular catalysis. A, Chemical》1998,130(3):128-240
Kinetic and catalytic aspects of DMT transesterification reaction, key step in the industrial production of polyethylenterephtalate (PET), have been deepened also through the use of model molecules such as CH3COO–Ph–X. These molecules give the same reactions with ethylene glycol occurring in the DMT transesterification too. The use of model molecules in the study of this reaction seems therefore to be promising in perspective. As we observed, however, the nature of the para-substituent X has a very strong influence on the reaction rate, when salts of bivalent metals such as Zn, Cd, Co, Mg, Mn, are used as catalysts, while this influence is much smaller when a tetravalent metal, as Ti, is used. This fact suggests that the transesterification mechanism operating in the two cases is different and this suggestion has been confirmed by applying Hammett's approach to the available kinetic data. Experimental kinetic runs were all performed at 193°C, by withdrawing small samples of the reaction mixture at different reaction times. These samples were gaschromatographically analyzed. We found volcano shaped curves of the reaction rates as a function of the metal ion acidities and we obtained different trends with a maximum of activity shifted from a metal to another for different substrates. A comparison of the kinetic results obtained, respectively, with the model molecules and DMT will be reported too. 相似文献
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Daniele Passarella Sergio Riva Gabriele Grieco Francesco Cavallo Begoña Checa Federica Arioli Elena Riva Daniela Comi Bruno Danieli 《Tetrahedron: Asymmetry》2009,20(2):192-197
The convenient synthesis of both enantiomers of the piperidine alkaloids such as dumetorine and epidihydropinidine is described. Pure enantiomers of 2-(2-hydroxy-ethyl)-piperidine-1-carboxylic acid tert-butyl ester are used as a common starting material. The syntheses are based on a RCM reaction and on methylation of the piperidine ring according to Beak–Lee methodology, respectively. 相似文献
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Pierpaolo Caricato Gianpaolo Ghiani Antonio Grieco Roberto Musmanno 《European Journal of Operational Research》2007
The single loop material flow system design is a combinatorial optimization problem, arising in material handling system design, which amounts to designing an unidirectional loop flow pattern as well as to locate pickup and delivery stations. The objective is to minimize the time required to carry out all material flow movements between cells. In this paper, we develop valid inequalities for a previously proposed formulation. The valid inequalities are then embedded into a branch-and-cut framework which is shown to solve much larger instances to optimality than those reported in the literature. A tailored tabu search heuristic is also illustrated and computationally assessed. 相似文献
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Antonello Santini Ettore Benedetti Carlo Pedone Giuseppe Caliendo Vincenzo Santagada Paolo Grieco Elisa Perissutti 《Structural chemistry》1996,7(3):173-181
The solid-state molecular conformations and crystal structures of three analogues of the CP-96,345 molecule, an important nonpeptidic SP antagonist, namely the (±)-2-(3-phenylbenzilidene)-3-(2-benzylamino) quinuclidine, theo-chloro- and theo-methoxy-derivatives, have been determined by X-ray diffusion analyses and refined to finalR values of 0.055, 0.045, and 0.056, respectively. All three molecules in the solid state show the same disposition of the substituents of the double bond and differences in the conformation mainly caused by the need of releasing intramolecular strains and/or nonbonded interactions. The observed molecular structures are compared to the reported solid-state structure of the CP-96,345 and correlated to the biological activity as NK antagonists. 相似文献
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Grazia Bencivenni Dr. Diana Salazar Illera Dr. Maria Moccia Prof. K. N. Houk Dr. Joseph A. Izzo Dr. Johanna Novacek Prof. Paolo Grieco Prof. Mathew J. Vetticatt Prof. Mario Waser Prof. Mauro F. A. Adamo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(44):11352-11366
Chiral phase-transfer catalysis provides high level of enantiocontrol, however no experimental data showed the interaction of catalysts and substrates. 1H NMR titration was carried out on Cinchona and Maruoka ammonium bromides vs. nitro, carbonyl, heterocycles, and N−F containing compounds. It was found that neutral organic species and quaternary ammonium salts interacted via an ensemble of catalyst +N−C−H and (sp2)C−H, specific for each substrate studied. The correspondent BArF salts interacted with carbonyls via a diverse set of +N−C−H and (sp2)C−H compared to bromides. This data suggests that BArF ammonium salts may display a different enantioselectivity profile. Although not providing quantitative data for the affinity constants, the data reported proofs that chiral ammonium salts coordinate with substrates, prior to transition state, through specific C−H positions in their structures, providing a new rational to rationalize the origin of enantioselectivity in their catalyses. 相似文献
9.
Caliendo Giuseppe Fiorino Ferdinando Grieco Paolo Perissutti Elisa Albrizio Stefania Giordano Marialuisa Santagada Vincenzo Santini Antonello 《Structural chemistry》1998,9(2):121-127
With the aim of discovering new molecules with K+ channel modulating properties, we have synthesized analogues of cromakalim, an important molecule which shows specific affinity toward the K+ channels, by replacing the benzopyrane ring with a benzoxazine moiety. As a part of this study, we have synthesized and characterized, in solution and in the solid state as well, the compound ethyl [2,2-dimethyl-6-(2-thiazolin-2-yl)-4H-l,4-benzoxazin-3-one-4-yl]butyrate (V). This compound exhibits in the solid state the following parameters: molecular formula C19H24N2O4S, triclinic, space group
, Mw = 376.5, a = 12.581(3) Å, b = 5.485(4) Å, c = 14.612(2) Å, = 91.85(2), = 108.9(3), = 82.04(4), V = 944.7 Å3, Z = 2, d = 1.323 g·cm–3. We describe here the synthesis and discuss the solid-state conformation of this new molecule; when tested on rat aorta ring precontracted with phenylephrine, the compound showed a concentration-dependent relaxation comparable to that measured for cromakalin taken as reference drug. 相似文献
10.
Isabel M. Gomez-Monterrey Alessia Bertamino Maria V. Diurno Paolo Grieco 《Tetrahedron》2006,62(34):8083-8088
A novel synthetic route of diaza-bridged heterocycles based on natural 3,9-diazabicyclo[3.3.1]non-6-ene scaffold has been accomplished. The synthetic approach consists of a Pictet-Spengler condensation of the l-Dopa-OMe with an appropriate aldehyde, Fmoc-Aa-H, followed by intramolecular lactamization. This approach generated two configurationally distinct products (cis and trans-isomers), increasing the stereochemical diversity of these compounds. The synthesized compounds are potentially useful in the discovery of novel pharmacologically active compounds. 相似文献