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Raab V Harms K Sundermeyer J Kovacević B Maksić ZB 《The Journal of organic chemistry》2003,68(23):8790-8797
1,8-bis(dimethylethyleneguanidino)naphthalene (DMEGN), the second example of a peralkyl guanidine "proton sponge" based on the 1,8-naphthalene backbone, was prepared and fully characterized. The crystal structure analysis of monoprotonated DMEGN reveals an unsymmetrical intramolecular hydrogen bridge. A decrease in the basicity with respect to the noncyclic parent 1,8-bis(tetramethylguanidino)naphthalene was found. Nevertheless, a new proton sponge provides a new crossbar in the ladder of highly basic neutral organic compounds. A detailed theoretical study of DMEGN and related cyclic guanidines explains this surprising experimental result. Homodesmotic reactions reveal that the intramolecular hydrogen bond contributes effectively 10 kcal/mol to proton affinity of DMEGN. 相似文献
13.
The performance of a new separation technique for metal-speciation — capillary electrophoresis (CE) — is presented. Polyhydroxy compounds such as polyphenols and organic tanning agents can be determined in the g/L range. Certain complexes of these compounds with iron (III) ions may also be directly or indirectly verified. The work has shown that it is possible to determine certain complexes existing in beverages (tea and coffee) by decomplexation with chelating agents (CDTA). The ligands released can be separated by CE and identified by their migration time and UV/VIS absorption spectra. 相似文献
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Hauke Harms Julien Rime Olivier Leupin Stephan J. Hug Jan Roelof van der Meer 《Mikrochimica acta》2005,151(3-4):217-222
A luminescent bacterial biosensor was used to quantify bioavailable arsenic in artificial groundwater. Its light production
above the background emission was proportional to the arsenite concentration in the toxicologically relevant range of 0 to
0.5 μM. Effects of the inorganic solutes phosphate, Fe(II) and silicate on the biosensor signal were studied. Phosphate at
a concentration of 0.25 g L−1 phosphate slightly stimulated the light emission, but much less than toxicologically relevant concentrations of the much
stronger inducer arsenite. No effect of phosphate was oberved in the presence of arsenite. Freshly prepared sodium silicate
solution at a concentration of 10 mg L−1 Si reduced the arsenite-induced light production by roughly 37%, which can be explained by transient polymerization leading
to sequestration of some arsenic. After three days of incubation, silicate did not have this effect anymore, probably because
depolymerization occurred. In the presence of 0.4 mg L−1 Fe(II), the arsenite-induced light emission was reduced by up to 90%, probably due to iron oxidation followed by arsenite
adsorption on the less soluble Fe(III) possibly along with some oxidation to the stronger adsorbing As(V). Addition of 100 μM
EDTA was capable of releasing all arsenic from the precipitate and to transform it into the biologically measurable, dissolved
state. The biosensor also proved valuable for monitoring the effectiveness of an arsenic removal procedure based on water
filtration through a mixture of sand and iron granules. 相似文献
17.
Intramolecular FeII-catalyzed reactions of various unsaturated alkoxycarbonyl azides are described. The reactions occur in the presence of stoichiometric amounts of trimethyl silyl chloride employing ethanol as the solvent. The corresponding 2-alkenyloxycarbonyl azides 5, 9, 18, 20, 22, and 24 gave the products 7/8, 10/11, 19, 21, 23, and 25 of an olefin chloroamination in moderate to good yields (47-72%). The facial diastereoselectivity of the ring closing C-N-bond forming step is good both in cyclic (20, 24) and in acyclic substrates (5, 18, 22) (>90% ds). The subsequent chlorine atom transfer occurs selectively in cyclic systems (20, 24) and in systems (9b, 18) which exhibit a conformational bias in the postulated radical intermediate 14. The lifetime tau of this elusive intermediate was estimated from the loss of stereochemical information in conformationally unrestricted systems (9a, 22) and from the data obtained with a radical clock (31-->32). 2-Alkynyloxycarbonyl azides 34 and 36 also yield chloroamination products which are obtained exclusively as the (Z)-isomers 35 and 37 (81-99% yield). The products of the tert-butyl-substituted substrates 38 undergo an immediate rearrangement/solvolysis reaction in the reaction mixture and gave the 5-alkoxyoxazolidinones 39 (93-99% yield). 相似文献
18.
Dr. Eduard Baal Marius Klein Dr. Klaus Harms Prof. Dr. Jörg Sundermeyer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(49):12610-12618
The synthesis of 2,9-diaza-1,3,8,10-tetratriflato-dibenzoperylene (DDP 3 a ) and corresponding 2,9-dimethyl-1,3,8,10-tetratriflato-dibenzoperylene (DBP 3 b ) has been developed at multigram scale via reduction of one of the industrially most important high-performance dyes, perylene-3,4,9,10-tetracarboxylic diimide (PTCDI), and of the corresponding dihydroxy peropyrenequinone precursor. The focus of this paper is on the reactivity pattern of 3 a as key intermediate towards highly functionalized 2,9-diazadibenzopyrelenes (DDPs) obtained via catalytic substitution of four triflate by aryl, heteroaryl, alkynyl, aminyl, and O-phosphanyl substituents. The influence of electron-donating substituents (OSiMe3, OPt-Bu2, N-piperidinyl), electron-withdrawing (OTf, 3,5-bis-trifluoromethyl-phenyl), and of electron-rich π-conjugated (2-thienyl, 4-tert-butylphenyl, trimethylsilyl-ethynyl) substituents on optoelectronic and structural properties of these functionalized DDPs has been investigated via XRD analyses, UV/Vis, PL spectroscopy, and by electroanalytical CV. These results were correlated to results of DFT and TD-DFT calculations. Thus, functionalized DPPs with easily tunable HOMO and LUMO energies and gap became available via a new and reliable synthetic strategy starting from readily available PTCDI. 相似文献
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Octahedral Chiral‐at‐Metal Iridium Catalysts: Versatile Chiral Lewis Acids for Asymmetric Conjugate Additions 下载免费PDF全文
Xiaodong Shen Haohua Huo Chuanyong Wang Bo Zhang Dr. Klaus Harms Prof. Dr. Eric Meggers 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(27):9720-9726
Octahedral iridium(III) complexes containing two bidentate cyclometalating 5‐tert‐butyl‐2‐phenylbenzoxazole ( IrO ) or 5‐tert‐butyl‐2‐phenylbenzothiazole ( IrS ) ligands in addition to two labile acetonitrile ligands are demonstrated to constitute a highly versatile class of asymmetric Lewis acid catalysts. These complexes feature the metal center as the exclusive source of chirality and serve as effective asymmetric catalysts (0.5–5.0 mol % catalyst loading) for a variety of reactions with α,β‐unsaturated carbonyl compounds, namely Friedel–Crafts alkylations (94–99 % ee), Michael additions with CH‐acidic compounds (81–97 % ee), and a variety of cycloadditions (92–99 % ee with high d.r.). Mechanistic investigations and crystal structures of an iridium‐coordinated substrates and iridium‐coordinated products are consistent with a mechanistic picture in which the α,β‐unsaturated carbonyl compounds are activated by two‐point binding (bidentate coordination) to the chiral Lewis acid. 相似文献