2-Chloro- and 2-bromo-1,1-diferrocenylcyclopropanes were synthesized as Z- and E-isomers with respect to the ferrocenyl substituent having a bisector orientation. The structure of Z-2-chloro-1,1-diferrocenylcyclopropane was confirmed by X-ray diffraction analysis. Treatment of the resulting monohalides with potassium tert-butoxide in dimethyl sulfoxide afforded 3,3-diferrocenylcyclopropene in 20% yield. The small ring in halogen-substituted diferrocenylcyclopropanes and diferrocenylcyclopropene is readily cleaved to give predominantly 3-ferrocenyl-1H-cyclopentaferrocene. 相似文献
The IR and NMR study of twelve 3- (or 5-) azidopyrazoles shows that the azide is the only tautomer present under neutral conditions. The most stable isomer (tautomer) is 3-azido in N-acetyl and N-H derivatives. 3-Azidopyrazoles are the only polyazoles in which coupling with the N-H in NMR (solvent: DMSO) is observed. In a basic medium, the corresponding anions of the 3-azidopyrazoles N-H are formed: these anions slowly evolve, following first-order kinetics, to the bicyclic anions of pyrazolo-[1,5-d] tetrazoles, derived from 3a-azapentalene. This evolution has been checked by means of IR and NMR spectroscopy. 相似文献
Poly(ethylene glycols) with molecular weights of approximately 1000 and 1500, which are commonly used in the preparation of polyether-urethanes, have been thermally degraded and a detailed analysis made of the volatile products using, principally, ir and mass spectrometry, glc and GC-MS. These products have been accounted for in terms of a concerted radical mechanism initiated by random scission of CO and CC bonds in the polymer chains. Two products, water and ethylene glycol, are more probably formed in independent reactions at chain terminal structures. 相似文献
The cocondensation reaction of lithium atoms and pure anisole leads to an ortho CH activation and the formation of lithium hydride. This simple two-component system allows the investigation of the reaction mechanism with included donor molecules. Therefore two anisole and one dilithium molecule, which was identified in an earlier spectroscopic study, were considered for the reaction pathway calculations.Firstly, two intermediates can be found along the reaction pathway, which show the reaction before and after the critical CH activation step. Secondly, a low-lying transition state can be identified, which allows the carbon hydrogen bond to be broken with an activation energy of less than 20 kcal/mol instead of more than 100 kcal/mol, if a free radical mechanism is employed. All calculations were performed at the B3LYP/6-31G** level of theory. 相似文献
High-throughput screening (HTS) of large compound collections typically results in numerous small molecule hits that must be carefully evaluated to identify valid drug leads. Although several filtering mechanisms and other tools exist that can assist the chemist in this process, it is often the case that costly synthetic resources are expended in pursuing false positives. We report here a rapid and reliable NMR-based method for identifying reactive false positives including those that oxidize or alkylate a protein target. Importantly, the reactive species need not be the parent compound, as both reactive impurities and breakdown products can be detected. The assay is called ALARM NMR (a La assay to detect reactive molecules by nuclear magnetic resonance) and is based on monitoring DTT-dependent (13)C chemical shift changes of the human La antigen in the presence of a test compound or mixture. Extensive validation has been performed to demonstrate the reliability and utility of using ALARM NMR to assess thiol reactivity. This included comparing ALARM NMR to a glutathione-based fluorescence assay, as well as testing a collection of more than 3500 compounds containing HTS hits from 23 drug targets. The data show that current in silico filtering tools fail to identify more than half of the compounds that can act via reactive mechanisms. Significantly, we show how ALARM NMR data has been critical in identifying reactive compounds that would otherwise have been prioritized for lead optimization. In addition, a new filtering tool has been developed on the basis of the ALARM NMR data that can augment current in silico programs for identifying nuisance compounds and improving the process of hit triage. 相似文献
Supramolecular dendrimers resulting from the dimerization of fullerene-functionalized dendrons through a quadruple hydrogen-bonding motif were prepared. The synthetic strategy is based on the esterification of a tert-butoxycarbonyl (Boc)-protected 2-ureido-4-[1H]pyrimidinone precursor possessing an alcohol function with fullerodendrons bearing a carboxylic acid unit at the focal point. Subsequent acidic treatment to cleave the protecting group and reaction of the resulting amine with octylisocyanate affords the targeted compounds. As demonstrated by the results of MALDI-TOF mass spectrometry and 1H NMR spectroscopy, both of the 2-ureido-4-[1H]pyrimidinone derivatives form self-assembled dimers spontaneously through hydrogen-bonding interactions, thus leading to supramolecular structures containing two or ten fullerene moieties. 相似文献
Protein–protein interactions are an important element in the understanding of protein function, and chemical cross-linking shotgun mass spectrometry is rapidly becoming a routine approach to identify these specific interfaces and topographical interactions. Protein cross-link data analysis is aided by dozens of algorithm choices, but hindered by a lack of a common format for representing results. Consequently, interoperability between algorithms and pipelines utilizing chemical cross-linking remains a challenge. pepXML is an open, widely-used format for representing spectral search algorithm results that has facilitated information exchange and pipeline development for typical shotgun mass spectrometry analyses. We describe an extension of this format to incorporate cross-linking spectral search results. We demonstrate application of the extension by representing results of multiple cross-linking search algorithms. In addition, we demonstrate adapting existing pepXML-supporting software pipelines to analyze protein cross-linking results formatted in pepXML.
Optical second harmonic generation (SHG) spectroscopy is used to probe Si(001) following thermal decomposition of diborane at the surface. Incorporation of boron (B) at second layer substitutional sites at H-free Si(001) intensifies and redshifts the E1 SHG spectral peak, while subsequent H termination further intensifies and blueshifts E1, in sharp contrast to the effect of bulk B doping or nonsubstitutional B. Ab initio pseudopotential and semiempirical tight binding calculations independently reproduce these unique trends, and attribute them to the surface electric field associated with charge transfer to electrically active B acceptors, and rehybridization of atomic bonds. 相似文献
A number of calix[6]arenes bearing ureas at the upper rim positions of alternate rings 1, 3 and 5 were prepared and studied in detail by NMR spectroscopy and gel permeation chromatography. N-Unsubstituted ureas were shown to dimerize through a cyclic array of hydrogen bonds to give cylindrical cavities capable of encapsulating small molecules such as dichloromethane, benzene and fluorobenzene. Slow equilibria between dimer and monomer were observed in [D6]DMSO-CDCl3 mixtures. By contrast, N-substituted ureas are monomeric. All urea monomers with bulky O-substituents display a solvent-dependent, slow equilibrium between C3v and Cs cone conformations. 相似文献