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31.
Van Der Eycken E Appukkuttan P De Borggraeve W Dehaen W Dallinger D Kappe CO 《The Journal of organic chemistry》2002,67(22):7904-7907
Inter- and intramolecular hetero-Diels-Alder reactions in a series of functionalized 2(1H)-pyrazinones were investigated under controlled microwave irradiation. The cycloaddition reactions were efficiently performed in sealed tubes, utilizing either a combination of 1,2-dichloroethane and a thermally stable ionic liquid, or 1,2-dichlorobenzene as reaction medium. In all cases, a significant rate-enhancement using microwave flash heating as compared to thermal heating was observed. 相似文献
32.
The electron capture negative ion (ECNI) mass spectra of two complex mixtures of polychlorinated decanes (PCDe) and polychlorinated
dodecanes (PCDo) are presented. The number of isomers in these mixtures is still high but is drastically reduced in comparison
to technical products of chlorinated paraffins (CP), due to their fixed chain length. As a result, the mass spectra are simplified
and less complex. Different modes of negative ion formation were observed in the spectra of the PCDe and PCDo. [M+Cl]– adduct ions were the most abundant ions in the spectra of lower chlorinated molecules. Higher chlorinated isomers formed
prominently [M-Cl]– and [M-HCl]– fragments besides [M+Cl]–. Possible consequences for the determination of chlorinated paraffins by ECNI-MS that result from the variation in ion formation
are addressed.
Received: 18 August 1997 / Revised: 26 January 1998 / Accepted: 31 January 1998 相似文献
33.
Chiral carbenium ions can be attacked by arene nucleophiles with high facial diastereoselectivity (dr >/= 94/6). Benzylic cations, such as 2, were generated under acidic conditions and reacted with arenes in intra- and intermolecular Friedel-Crafts alkylation reaction. The depicted reaction 1 --> 3 represents one example for the unprecedented, highly diastereoselective intermolecular Friedel-Crafts alkylation reactions which were observed in this study. 相似文献
34.
Kratzsch C Tenberken O Peters FT Weber AA Kraemer T Maurer HH 《Journal of mass spectrometry : JMS》2004,39(8):856-872
A liquid chromatographic/mass spectrometric assay with atmospheric pressure chemical ionization (LC/APCI-MS) is presented for fast and reliable screening and identification and also for precise and sensitive quantification in plasma of the 23 benzodiazepines alprazolam, bromazepam, brotizolam, camazepam, chlordiazepoxide, clobazam, clonazepam, diazepam, flunitrazepam, flurazepam, desalkylflurazepam, lorazepam, lormetazepam, medazepam, metaclazepam, midazolam, nitrazepam, nordazepam, oxazepam, prazepam, temazepam and tetrazepam, triazolam, their antagonist flumazenil and the benzodiazepine BZ1 (omega 1) receptor agonists zaleplone, zolpidem and zopiclone. It allows confirmation of the diagnosis of an overdose situation and monitoring of psychiatric patients' compliance. The analytes were isolated from plasma using liquid-liquid extraction and were separated on a Merck LiChroCART column with Superspher 60 RP Select B as the stationary phase. Gradient elution was performed using aqueous ammonium formate and acetonitrile. After screening and identification in the scan mode using the authors' LC/MS library, the analytes were quantified in the selected-ion monitoring mode. The quantification assay was fully validated. It was found to be selective proved to be linear from sub-therapeutic to over therapeutic concentrations for all analytes, except bromazepam. The corresponding reference levels the assay's accuracy and precision data for all studied substances are listed. The accuracy and precision data were within the required limits with the exception of those for bromazepam. The analytes were stable in frozen plasma for at least 1 month. The validated assay was successfully applied to several authentic plasma samples from patients treated or intoxicated with various benzodiazepines or with zaleplone, zolpidem or zopiclone. It has proven to be appropriate for the isolation, separation, screening, identification and quantification of the drugs mentioned above in plasma for clinical toxicology, e.g. in cases of poisoning, and forensic toxicology, e.g. in cases of driving under the influence of drugs. 相似文献
35.
Elke Barsties Stefan Schaible Marc-Heinrich Prosenc Ursula Rief Werner Rll Oliver Weyand Birgit Dorer Hans-Herbert Brintzinger 《Journal of organometallic chemistry》1996,520(1-2):63-68
Bis(2-N,N-dimethylamino-indenyl) zirconium dichloride, (2-(CH3)2N-C9H6)2ZrCl2, and dimethylsilyl-bridged bis(2-N,N-dimethylamino-indenyl) zirconium dichloride, (CH3)2Si(2-(CH3)2N-C9H5)2ZrCl2, were prepared by reaction of the corresponding ligand lithium salts with ZrCl4 in toluene. Diffractometric structure determinations reveal C2-symmetric complex geometries for both complexes. An increased electron density at the Zr center of the dimethylamino-substituted complexes is indicated by reduction potentials which are 0.3–0.4 V more negative than those of their unsubstituted analogs. When activated with methyl aluminoxane in toluene solution, (CH3)2Si(2-(CH3)2N-C9H5)2ZrCl2 catalyzes the polymerization of propene to polymers with a microstructure comparable with that of polymers produced with other Me2Si-bridged bis(indenyl)ZrCl2 complexes, but with a substantially increased fraction of i-propyl end groups derived from alkyl exchange between Zr-polymer and Al---Me species. 相似文献
36.
The intramolecular cyclization reactions of tri-1-hex-5-enyl Group III derivatives and of 1-hex-5-enyllithium have been investigated and it is proposed that the reactions may be depicted as internal addition across the terminal double bonds of the alkenyl species. The cyclization reaction proceeds more readily for the 1-hex-5-enyl derivatives than for any other chain length and is dependent on temperature, concentration and solvent. 1H NMR data and cryoscopic molecular weight data are presented for several diisobutyialkenyl- and diisobutylalkyl-aluminum derivatives. These data have been interpreted in terms of a direct intramolecular interaction between the metal center and the π-electron system of the olefinic site. The intramolecular cyclization reactions for the 1-hept-6-enyl, 1-oct-7-enyl- and 1-undec-10-enylaluminum derivatives also were investigated and it was found that cyclization occurred only for the 1-hept-6-enyl derivative. 相似文献
37.
A hybrid multiplex microarray microsystem has been developed that consists of 32 individually addressable array reaction chambers, supporting the use of multichannel pipettes for addition of up to 8 samples simultaneously. Discrimination between Campylobacter jejuni and Campylobacter coli bacteria was observed in DNA samples containing Campylobacter spp., with the same specificity and sensitivity as when compared to a full-size microarray. The spinloaded multiplex microarray microsystem described provides a novel and convenient test format for simultaneous low-density microarray analysis and is universally adaptable to other DNA, protein or small molecule microarray based applications. 相似文献
38.
Concise total syntheses of the bioactive mesotricyclic diterpenoids jatrophatrione and citlalitrione
The highly functionalized [5.9.5] tricyclic framework resident in jatrophatrione (1) and citlalitrione (2) has been synthesized. The route begins with the tandem anionic oxy-Cope rearrangement/methylation/transannular ene cyclization of 21 and subsequent introduction of a conjugated enone double bond. Hydroxyl-directed 1,4-reduction of this functionality in 25 with LiAlH(4)/CuI/hexamethylphosphoramide/tetrahydrofuran sets the stage for the implementation of a Grob fragmentation and expedited generation of 27. Stereocontrolled intramolecular hydrosilylation allows for the subsequent introduction of a cyclic carbonate as in 53. This intermediate undergoes remarkably efficient, fully regiocontrolled Treibs reaction to generate 54, with this maneuver serving as a pivotal step for making 1 available five steps later. Treatment of 1 with m-chloroperbenzoic acid leads to 2, with attack occurring preferentially on a alpha-face of the double bond more remote to the carbonyl. 相似文献
39.
Bolm C Verrucci M Simic O Cozzi PG Raabe G Okamura H 《Chemical communications (Cambridge, England)》2003,(22):2826-2827
Quinoline-based C1-symmetric sulfoximines have been used as chiral ligands in copper-catalyzed asymmetric hetero Diels-Alder reactions leading to cycloadducts with up to 96% ee. 相似文献
40.
Inderwildi OR Lebiedz D Deutschmann O Warnatz J 《The Journal of chemical physics》2005,122(15):154702
In this study, density functional theory calculations were performed to investigate the influence of oxygen preoccupation on the nitrogen oxide decomposition on rhodium. Besides gauging the coverage dependence of the adsorption energy of NO on the (111) rhodium facet, the influence of the initial oxygen coverage on the kinetics and thermodynamics of the nitrogen oxide decomposition reaction was also studied. The results are discussed with respect to a novel NOx decomposition catalyst. Furthermore, the influence of spin effects on the adsorption geometry as well as the adsorption energy is examined. It will be addressed why spin effects only have a minor influence on the behavior of NO on a rhodium surface. 相似文献