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21.
Banti D Belokon' YN Fu WL Groaz E North M 《Chemical communications (Cambridge, England)》2005,(21):2707-2709
Hammett data indicate that the asymmetric alkylation of enolates catalysed by copper(II)salen complex 1, proceeds by an asynchronous S(N)2 reaction and that the role of the catalyst is to enhance the nucleophilicity of the enolate. 相似文献
22.
Arduini A Brindani E Giorgi G Pochini A Secchi A 《The Journal of organic chemistry》2002,67(17):6188-6194
A novel heteroditopic receptor (5) based on a rigid calix[4]arene cavity bearing at the upper rim four arylsulfonamido binding sites has been synthesized. The binding abilities of this new host have been investigated in apolar solvents toward a series of tetramethylammonium salts (tosylate, chloride, acetate, trifluoroacetate, and picrate) and compared with those of monotopic and heteroditopic calix[4]arene-bis(crown-3)-based receptors 1 and 2 in order to evaluate the role of the anion on ion-pair recognition. While monotopic host 1 shows an efficiency order toward the different salts that increases when the anion is less interactive (Hofmeister trend), an opposite role of the counteranion on the recognition process was observed with host 5 (anti-Hofmeister trend). A more complex behavior is experienced by host 2, which shows a high and leveled efficiency for all the anions tested. The results obtained were explained on the basis of the different types of ion pairs present in the recognition process. Further information on the role of the anion were obtained by the "dual host" strategy utilizing the tri-n-butylthioureido derivative of tren 7, which forms a stable complex with chloride anion. The very high efficiency shown by these heteroditopic hosts opens new routes in supramolecular projects and is a very interesting tool in the molecular recognition of ion-pairs and its applications. 相似文献
23.
Nine samples of N-acetyl-3,4-methylenedioxyamphetamine (N-acetyl-MDA), prepared according to the most common synthetic procedures, are submitted to (2)H NMR spectroscopy. The relative deuterium content at the various sites of the molecule is shown to depend on its synthetic history. The technique provides a chemical fingerprint of N-acetyl-MDAs and it can be used to trace back the precursor materials and the synthetic pathways employed in the preparation of the samples. 相似文献
24.
Aresta M Dibenedetto A Fracchiolla E Giannoccaro P Pastore C Pápai I Schubert G 《The Journal of organic chemistry》2005,70(16):6177-6186
Dicyclohexylcarbodiimide (CyN=C=NCy, DCC) promotes the facile formation of organic carbonates from aliphatic alcohols and carbon dioxide at temperatures as low as 310 K and moderate pressure of CO2 (from 0.1 MPa) with an acceptable rate. The conversion yield of DCC is quantitative, and the reaction has a very high selectivity toward carbonates at 330 K; increasing the temperature increases the conversion rate, but lowers the selectivity. A detailed study has allowed us to isolate or identify the intermediates formed in the reaction of an alcohol with DCC in the presence or absence of carbon dioxide. The first step is the addition of alcohol to the cumulene (a known reaction) with formation of an O-alkyl isourea [RHNC(OR')=NR] that may interact with a second alcohol molecule via H-bond (a reaction never described thus far). Such an adduct can be detected by NMR. In alcohol, in absence of CO2, it converts into a carbamate and a secondary amine, while in the presence of CO2, the dialkyl carbonate, (RO)2CO, is formed together with urea [CyHN-CO-NHCy]. The reaction has been tested with various aliphatic alcohols such as methanol, ethanol, and allyl alcohol. It results in being a convenient route to the synthesis of diallyl carbonate, in particular. O-Methyl-N,N'-dicyclohexyl isourea also reacts with phenol in the presence of CO2 to directly afford for the very first time a mixed aliphatic-aromatic carbonate, (MeO)(PhO)CO. A DFT study has allowed us to estimate the energy of each intermediate and the relevant kinetic barriers in the described reactions, providing reasonable mechanistic details. Calculated data match very well the experimental results. The driving force of the reaction is the conversion of carbodiimide into the relevant urea, which is some 35 kcal/mol downhill with respect to the parent compound. The best operative conditions have been defined for achieving a quantitative yield of carbonate from carbodiimide. The role of temperature, pressure, and catalysts (Lewis acids and bases) has been established. As the urea can be reconverted into DCC, the reaction described in this article may further be developed for application to the synthesis of organic carbonates under selective and mild conditions. 相似文献
25.
Favero G Campanella L Cavallo S D'Annibale A Perrella M Mattei E Ferri T 《Journal of the American Chemical Society》2005,127(22):8103-8111
The realization of a reliable receptor biosensor requires stable, long-lasting, reconstituted biomembranes able to supply a suitable biomimetic environment where the receptor can properly work after incorporation. To this end, we developed a new method for preparing stable biological membranes that couple the biomimetic properties of BLMs (bilayer lipid membranes) with the high stability of HBMs (hybrid bilayer membranes); this gives rise to an innovative assembly, named MHBLM (mixed hybrid bilayer lipid membrane). The present work deals with the characterization of biosensors achieved by embedding an ionotropic glutamate receptor (GluR) on MHBLM. Thanks to signal (transmembrane current) amplification, which is typical of natural receptors, the biosensor here produced detects glutamate at a level of nmol L(-1). The transmembrane current changes linearly vs glutamate up to 100 nmol L(-1), while the limit of detection is 1 nmol L(-1). In addition, the biosensor response can be modulated both by receptor agonists (glycine) and antagonists (Mg(2+)) as well, and by exploiting the biosensor response, the distribution of different kinds of ionotropic GluR present in the purified sample, and embedded in MHBLM, was also evaluated. Finally, one of the most important aspects of this investigation is represented by the high stability of the biomimetic system, which allows the use of biosensor under flowing conditions, where the solutions flow on both biomembrane faces. 相似文献
26.
Agnese Abate Elisabetta Brenna Giovanni Fronza Claudio Fuganti FrancescoG. Gatti Stefano Serra Enrica Zardoni 《Helvetica chimica acta》2004,87(4):765-780
All the enantiomerically enriched stereoisomers of Clarycet ® ( 1 ), Florol ® ( 2 ), and Rhubafuran ® ( 3 ) were prepared by biocatalysis routes. Their absolute configurations were established, and their olfactory properties were fully evaluated. 相似文献
27.
Castagnola M Zuppi C Rossetti DV Vincenzoni F Lupi A Vitali A Meucci E Messana I 《Electrophoresis》2002,23(12):1769-1778
The general properties of dendrimers and in particular their electrolytic characteristics that are relevant in electrokinetic separations, are described. In order to confirm theoretical considerations on commercial dendrimer charge and hydrodynamic radius, several capillary zone electrophoresis (CZE) experiments were performed. Electrophoretic mobilities measured at different pH values indicated a sensible increase of dendrimer hydrodynamic radius at pH values lower than 2.5. This was probably due to the Coulombic repulsion of charged amine groups of the inner dendrimer shells. The principal reasons that should address the use of dendrimers as pseudostationary phases in micellar electrokinetic chromatography (MEKC) are discussed. Moreover, a survey of different separations performed utilizing dendrimers in MEKC as well as of several future plausible uses of various classes of dendrimers is presented. 相似文献
28.
Laganà A Curini R D'Ascenzo G De Leva I Faberi A Pastorini E 《Rapid communications in mass spectrometry : RCM》2003,17(10):1037-1043
A reliable, sensitive and selective liquid chromatography/tandem mass spectrometry (LC/MS/MS) method has been developed to determine four trichothecene mycotoxins (nivalenol, deoxynivalenol, fusarenon X and 3-acetyldeoxynivalenol) in maize. Sample preparation was performed by extracting the analytes with a mixture of acetonitrile and water, followed by a solid-phase extraction with Carbograph-4 cartridges as the purification step. For the LC/MS/MS analysis two interfacing systems, Turbo IonSpray (TISP) and atmospheric pressure chemical ionization (APCI), were compared in both negative and positive ion modes. LC and MS parameters were optimized to achieve better results and sensitivity. The effect of mobile phase modifiers such as ammonium acetate and formic acid on the ionization yield was also evaluated. The best results were obtained using the electrospray ionization (ESI) interface in negative ion mode and the multiple reaction monitoring mode (MRM) for the quantitation. The detection limits ranged between 10 ng/g for fusarenon X and 1.5 ng/g for deoxynivalenol. A linear working range was achieved with a standard deviation between 3 and 10% and recovery rates from the maize samples above 81%. The procedure was applied to the analysis of a set of maize samples collected from farms located in different areas of northern and central Italy. The investigated samples turned out to be contaminated primarily with deoxynivalenol and, to a minor extent, with its derivatives. 相似文献
29.
Bartoli G Bartolacci M Bosco M Foglia G Giuliani A Marcantoni E Sambri L Torregiani E 《The Journal of organic chemistry》2003,68(11):4594-4597
Alkylation of indoles by means of the Michael addition has been the subject of a number of investigation. It is well established that regioselectivity in the additions of indoles to electron-deficient alkenes is strongly controlled by the reaction medium. In a continuation of the work on developing greener and cleaner technologies, the cerium(III) chloride heptahydrate and sodium iodide combination supported on silica gel catalyzes the alkylation of various indoles with alpha,beta-unsaturated ketones giving 3-(3-oxoalkyl)indole derivatives in good yields. The substitution on the indole nucleus occurred exclusively at the 3-position, and N-alkylation products have not been observed. 相似文献
30.
Armaroli N Marconi G Echegoyen L Bourgeois JP Diederich F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(9):1629-1645
The cyclophane-type molecular dyads 1 x 2H and 1 x Zn, in which a doubly bridged porphyrin donor adopts a close, tangential orientation relative to the surface of a fullerene acceptor, were prepared by Bingel macrocylization. The porphyrin derivatives 2 x 2H and 2 x Zn with two appended, singly linked C60 moieties were also formed as side products. NMR investigations revealed that the latter compounds strongly prefer conformations with one of the carbon spheres nesting on the porphyrin surface, thereby taking a similar orientation to that of the fullerene moiety in the doubly bridged systems. Cyclic voltammetric measurements showed that the mutual electronic effects exerted by the fullerene on the porphyrin and vice versa are only small in all four dyads, despite the close proximity of the donor and acceptor components. The steady-state and time-resolved absorption and luminescence properties of 1 x Zn and 2 x Zn were investigated in toluene solution and it was shown that, upon light excitation, both the porphyrin- and the fullerene-centered excited states are deactivated to a lower-lying CT state, emitting in the IR spectral region (lambda max = 890 and 800 nm at 298 and 77 K, respectively). In the more polar solvent benzonitrile, this CT state is still detected but, owing to its very low energy (below 1.4 eV), is not luminescent and shorter-lived than in toluene. The remarkable observation of similar photophysical behavior of 1 x Zn and 2 x Zn suggests that a tight donor-acceptor distance cannot only be established in doubly bridged cyclophane-type structures but also in singly bridged dyads, by taking advantage of favourable fullerene-porphyrin ground-state interactions. 相似文献