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71.
Carbery DR Reignier S Miller ND Adams H Harrity JP 《The Journal of organic chemistry》2003,68(11):4392-4399
A stereocontrolled approach to alpha-alkyl beta-alkynyl cyclohexanones is reported through a Lewis acid mediated rearrangement reaction of enol ethers bearing an Co-alkyne moiety. The reaction proceeds with high levels of stereoselectivity in the presence of Ti- and B-Lewis acids to provide a range of alpha,beta-disubstituted cyclohexanones in high yield although the products are prone to epimerization at the alpha-position in the presence of the B-promoter system. The potential for an enantioselective variant of this process is outlined, and a rationale for the observed stereochemical trends and detailed structural analyses of the ketone products are described. 相似文献
72.
73.
74.
Rushdi I. Yousef Tobias Rüffer Harry Schmidt Dirk Steinborn 《Journal of organometallic chemistry》2005,690(5):1178-1191
MgMe2 (1) was found to react with 1,4-diazabicyclo[2.2.2]octane (dabco) in tetrahydrofuran (thf) yielding a binuclear complex [{MgMe2(thf)}2(μ-dabco)] (2). Furthermore, from reactions of MgMeBr with diglyme (diethylene glycol dimethyl ether), NEt3, and tmeda (N,N,N′,N′-tetramethylethylenediamine) in etheral solvents compounds MgMeBr(L), (L = diglyme (5); NEt3 (6); tmeda (7)) were obtained as highly air- and moisture-sensitive white powders. From a thf solution of 7 crystals of [MgMeBr(thf)(tmeda)] (8) were obtained. Reactions of MgMeBr with pmdta (N,N,N′,N″,N″-pentamethyldiethylenetriamine) in thf resulted in formation of [MgMeBr(pmdta)] (9) in nearly quantitative yield. On the other hand, the same reaction in diethyl ether gave MgMeBr(pmdta) · MgBr2(pmdta) (10) and [{MgMe2(pmdta)}7{MgMeBr(pmdta)}] (11) in 24% and 2% yield, respectively, as well as [MgMe2(pmdta)] (12) as colorless needle-like crystals in about 26% yield. The synthesized methylmagnesium compounds were characterized by microanalysis and 1H and 13C NMR spectroscopy. The coordination-induced shifts of the 1H and 13C nuclei of the ligands are small; the largest ones were found in the tmeda and pmdta complexes. Single-crystal X-ray diffraction analyses revealed in 2 a tetrahedral environment of the Mg atoms with a bridging dabco ligand and in 8 a trigonal-bipyramidal coordination of the Mg atom. The single-crystal X-ray diffraction analyses of [MgMe2(pmdta)] (12) and [MgBr2(pmdta)] (13) showed them to be monomeric with five-coordinate Mg atoms. The square-pyramidal coordination polyhedra are built up of three N and two C atoms in 12 and three N and two Br atoms in 13. The apical positions are occupied by methyl and bromo ligands, respectively. Temperature-dependent 1H NMR spectroscopic measurements (from 27 to −80 °C) of methylmagnesium bromide complexes MgMeBr(L) (L = thf (4); diglyme (5); NEt3 (6); tmeda (7)) in thf-d8 solutions indicated that the deeper the temperature the more the Schlenk equilibria are shifted to the dimethylmagnesium/dibromomagnesium species. Furthermore, at −80 °C the dimethylmagnesium compounds are predominant in the solutions of Grignard compounds 4-6 whereas in the case of the tmeda complex7 the equilibrium constant was roughly estimated to be 0.25. In contrast, [MgMeBr(pmdta)] (9) in thf-d8 revealed no dismutation into [MgMe2(pmdta)] (12) and [MgBr2(pmdta)] (13) even up to −100 °C. In accordance with this unexpected behavior, 1:1 mixtures of 12 and 13 were found to react in thf at room temperature yielding quantitatively the corresponding Grignard compound 9. Moreover, the structures of [MgMeBr(pmdta)] (9c), [MgMe2(pmdta)] (12c), and [MgBr2(pmdta)] (13c) were calculated on the DFT level of theory. The calculated structures 12c and 13c are in a good agreement with the experimentally observed structures 12 and 13. The equilibrium constant of the Schlenk equilibrium (2 9c ? 12c + 13c) was calculated to be Kgas = 2.0 × 10−3 (298 K) in the gas phase. Considering the solvent effects of both thf and diethyl ether using a polarized continuum model (PCM) the corresponding equilibrium constants were calculated to be Kthf = 1.2 × 10−3 and Kether = 3.2 × 10−3 (298 K), respectively. 相似文献
75.
Selenium is determined in the ng g?1 to μg g?1 range in biological and environmental samples. A wet digestion procedure was optimized with respect to volatility losses and recovery yields, by using 75Se metabolically incorporated into rat organs. Selenium is preconcentrated from the digestion liquid by a two-step reduction with 4 M HCl and ascorbic acid. The colloidal selenium formed is adsorbed on activated carbon and filtered on a Nucleopore membrane for measurement by energy-dispersive x-ray fluorescence. Almost complete recovery was obtained, and the detection limit was 20 ng, corresponding to 10 ng g?1 for a 2-g sample. Biological reference materials were analyzed with satisfactory results, and the accuracy of the method was good. 相似文献
76.
Michels JJ O'Connell MJ Taylor PN Wilson JS Cacialli F Anderson HL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(24):6167-6176
A series of conjugated polyrotaxane insulated molecular wires are synthesised by aqueous Suzuki polymerisation, using hydrophobic binding to promote threading of the cyclodextrin units. These polyrotaxanes have conjugated polymer cores based on poly(para-phenylene), polyfluorene, and poly(diphenylene-vinylene), threaded through 0.9-1.6 cyclodextrins per repeat unit. Bulky naphthalene-3,6-disulfonate endgroups prevent the macrocycles from slipping off the conjugated polymer chains. Dialysis experiments show that the cyclodextrins become unthreaded only if smaller stoppers are used. MALDI TOF mass spectra detect oligomers with up to ten threaded cyclodextrins, and reveal the presence of some defects that result for oxidative homo-coupling of boronic acids. Weight-average molecular weights were determined by analytical ultracentrifugation, demonstrating that step-growth polymerisation is efficient enough to achieve degrees of polymerisation up to approximately 20 repeat units (84 para-phenylenes). The fluorescence spectra of these polyrotaxanes indicate that the presence of the threaded cyclodextrin macrocycles reduces the flexibility of the conjugated polymer pi-systems. Both the solution and the solid-state photoluminescence quantum yields are enhanced upon threading of the conjugated polyaromatic cores through alpha- or beta-cyclodextrins, and the emission spectra of the polyrotaxanes are blue-shifted compared to the corresponding unthreaded polymers. The greater weight of the 0-0 transition in the emission spectra, as well as the smaller Stokes shift, indicate that the polyrotaxanes are more rigid than the unthreaded polymers. 相似文献
77.
The synthesis of 2,4,6-cycloheptatrienethione ( 1 ) was accomplished by reaction of tropone and phosphorus pentasulfide. Although 1 proved to be extremely unstable in concentrated solution, its UV. spectrum was measured, the ε-values being determined indirectly by hydrolysis to tropone. The proof of structure rests on analytical data, conversion to tropone oxime on reaction with hydroxylamine and reaction with the sodium salt of malonitrile to give 2-amino-3-cyano-3aH-cyclohepta[b]thiophene ( 4 ) which rearranged on chromatography to give what is probably the corresponding 8H-compound ( 5 ). On dissolving 1 in 95% sulfuric acid, a large hypsochromic shift in the UV. spectrum was observed, which may be due to the mercaptotropylium ion. 相似文献
78.
Miller JE Grădinaru C Crane BR Di Bilio AJ Wehbi WA Un S Winkler JR Gray HB 《Journal of the American Chemical Society》2003,125(47):14220-14221
Near-UV irradiation of structurally characterized [Re(I)(CO)3(1,10-phenanthroline)(Q107H)](W48F/Y72F/H83Q/Y108W)AzM(II) [Az = Pseudomonas aeruginosa azurin, M = Cu, Zn]/[Co(NH3)5Cl]Cl2 produces a tryptophan radical (W108*) with unprecedented kinetic stability. After rapid formation (k = 2.8 x 106 s-1), the radical persists for more than 5 h at room temperature in the folded ReAzM(II) structure. The absorption spectrum of ReAz(W108*)M(II) exhibits maxima at 512 and 536 nm. Oxidation of K4[Mo(CN)8] by ReAz(W108*)Zn(II) places the W108*/W108 reduction potential in the protein above 0.8 V vs NHE. 相似文献
79.
Roy G. Miller Darryl R. Fahey Harry J. Golden Larry C. Satek 《Journal of organometallic chemistry》1974,82(1):127-137
Thermolysis of trans-chloro(2-allylphenyl)bis(triethylphosphine)nickel(II), I, in tetrachloroethylene has afforded indene as the major hydrocarbon product along with lesser amounts of allylbenzene and trans-β-methylstyrene. Organonickel products were trans-chloro(trichlorovinyl)bis(triethylphosphine)nickel(II), II, chloro[2-(trans-propenyl)phenyl]bis(triethylphosphine)nickel(II), III, and trans-dichlorobis(triethylphosphine)nickel(II). Compound III was the major product from thermolysis of I in benzene. Chloro[2-(cis-propenyl)phenyl]bis(triethylphosphine)nickel(II), IV, and III could be synthesized independently by treatment of chloro-2-(cis-propenyl)benzene and chloro-2-(trans-propenyl)benzene, respectively, with nickel acetylacetonate and triethylaluminium in the presence of triethylphosphine. Thermolysis of I in benzene containing allylbenzene led to the formation of trans-β-methylstyrene. The thermolysis of I in benzene in the presence of cis-1,4-hexadiene caused the skeletal rearrangement of the diene to trans-2-methyl-1,3-pentadiene. A catalyst derived from ethylenebis(triphenylphosphine)nickel(0) and hydrogen chloride isomerized allylbenzene to trans-β-methylstyrene. 相似文献
80.
Klaus Grasshoff und Harry Hahn 《Fresenius' Journal of Analytical Chemistry》1962,186(1):147-153
Zusammenfassung Es wird eine polarographische Methode zur Bestimmung von Molybdän in Stahl beschrieben. Als Trägerelektrolyt wird 0,1 m Citronensäure verwendet. Bei pH 2 treten zwei Stufen mit einem Halbstufenpotential von –0,27 und –0,65 V auf. Der Diffusionsstrom bzw. Spitzenstrom beider Stufen ist gut ausgebildet und gut reproduzierbar. Eisen sowie die üblichen in Stählen vorkommenden Elemente stören die Bestimmung nicht. Die Brauchbarkeit und die Genauigkeit der Methode wird an vier verschiedenen Legierungen mit Gehalten von 0,3–1,3% Molybdän demonstriert.V. Mitteilung: Grasshoff, K., u. H. Hahn: diese Z. 186, 132 (1962).Wir danken der Deutschen Forschungsgemeinschaft sowie dem Fonds der Chemischen Industrie für die Unterstützung dieser Arbeit. 相似文献