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211.
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
212.
Blake AJ Bencini A Caltagirone C De Filippo G Dolci LS Garau A Isaia F Lippolis V Mariani P Prodi L Montalti M Zaccheroni N Wilson C 《Dalton transactions (Cambridge, England : 2003)》2004,(17):2771-2779
The coordination chemistry of the new pyridine-based, N2S2-donating 12-membered macrocycle 2,8-dithia-5-aza-2,6-pyridinophane (L1) towards Cu(II), Zn(II), Cd(II), Hg(II), and Pb(II) has been investigated both in aqueous solution and in the solid state. The protonation constants for L1 and stability constants with the aforementioned metal ions have been determined potentiometrically and compared with those of ligand L2, which contains a N-aminopropyl side arm. The measured values show that Hg(II) in water has the highest affinity for both ligands followed by Cu(II), Cd(II), Pb(II), and Zn(II). For each metal ion considered, 1:1 complexes with L1 have also been isolated in the solid state, those of Cu(II) and Zn(II) having also been characterised by X-ray crystallography. In both complexes L1 adopts a folded conformation and the coordination environments around the two metal centres are very similar: four positions of a distorted octahedral coordination sphere are occupied by the donor atoms of the macrocyclic ligand, and the two mutually cis-positions unoccupied by L1 accommodate monodentate NO3- ligands. The macrocycle L1 has then been functionalised with different fluorogenic subunits. In particular, the N-dansylamidopropyl (L3), N-(9-anthracenyl)methyl (L4), and N-(8-hydroxy-2-quinolinyl)methyl (L5) pendant arm derivatives of L1 have been synthesised and their optical response to the above mentioned metal ions investigated in MeCN/H2O (4:1 v/v) solutions. 相似文献
213.
H. E. Miller H. Rsler A. Wohlpart H. Wyler M. E. Wilcox H. Frohofer T. J. Mabry Andr S. Dreiding 《Helvetica chimica acta》1968,51(6):1470-1474
During studies on the biogenesis of betalains (I) in cactus fruits (Opuntia sp.). DL -dopa-1-[14C] and -2-[14C] were incorporated into betanin (III) which was obtained radiopure after crystallization. The specific activity remained constant after conversion to betanidin (IV) and to a neobetanidin derivative (IX). Reaction of radiobetanin with proline afforded indicaxanthin (V) carrying more than 90% of the radioactivity. Dopa (VI) is thus an efficient precursor for betalamic acid (VIII) but not for cyclodopa (VII). Decarboxylation of radiobetanidin and radioindicaxanthin showed that the carboxyl group of dopa remained a carboxyl group in the biotransformation to betalamic acid. It is concluded that the aromatic ring of dopa is cleaved and that re-cyclization involving the nitrogen generates the dihydropyridine moiety. Under the same conditions mevalonic acid, aspartic acid and phenylalanine showed low incorporations. Studies with beet seedlings and DL -dopa-1-[14C], -2-[14C] and DL -tyrosine-1-[14C] afforded similar results but with low incorporations. 相似文献
214.
Joanna Szpunar-Łobińska Michiel Ceulemans Wilfried Dirkx Claudia Witte Ryszard Łobiński Freddy C. Adams 《Mikrochimica acta》1994,113(3-6):287-298
Interferences in trace and ultratrace speciation analysis of organotin and organolead compounds in various samples by gas chromatography coupled with atomic absorption spectrometry (AAS) and/or microwave induced plasma atomic emission spectrometry (MIP AES) are investigated. Particular attention is given to the effects of matrix co-extractives and reagents impurities introduced during sample preparation. Their influence on the detection limits is discussed in terms of baseline noise level, blank value, formation of artefacts and signal suppression. Loss of column resolution during the analysis of some matrices is observed. 相似文献
215.
Toluene diluted in argon subjected to continuous argon discharge radiation during condensation at 21 K revealed absorptions at 310.5 and 449.6 nm due to benzyl radical, and 317 nm due to a C77H9 radical. A photosensitive 430 nm band, in agreement with photodissociation spectra of the toluene parent cation, is assigned to this species. 相似文献
216.
A method for the determination of the dynamic surface tension of surfactant solutions is presented which allows to cover adsorption times down to 10 seconds. This method is based on the determination of the pressure inside two communicating bubbles. There is no deformation of the solution/air interface during the experimental procedure. Hence, in evaluating the kinetic data no surface area enlargement has to be taken into account. An automatically operating procedure should allow to cover adsorption times down to approximately one second and should improve the measuring accuracy substantially. Experimental investigations with aqueous n-decanoic acid solutions using the method proposed provided evidence that decanoic acid is adsorbed by a diffusioncontrolled mechanism. 相似文献
217.
Trimethylsilyl Derivatives of Vb Elements. VII. Crystal Structures of Lithium Bis(trimethylsilyl)bismuthide · DME and of Tetrakis(trimethylsilyl)dibismuthane as well as Some Comments on the Crystal Structure of Bis(4-methoxyphenyl)ditellane Colourless lithium bis(trimethylsilyl)bismuthide · DME 1 1,2-Dimethoxyethan (DME); Tetrahydrofuran (THF) 1 and green, metallic lustrous tetrakis(trimethylsilyl)dibismuthane 2 crystallize isotopic to their antimony homologues [1, 2]. As it is shown by crystal structure determinations { 1 : ?90°C; I 4 2d; a = 1017,3(4); c = 3738,0(26) pm; Z = 8; R w = 0,065; 2 : + 20°C; P2 1 /c; a = 680,9(4); b = 1704,8(13); c = 1197,9 (10) pm; β = 119,46(6)°; Z = 2; R w = 0,084} both compounds form chains which in the case of bismuthide 1 are built up as screws of alternating bismuth and lithium atoms; bonding further to two trimethylsilyl groups or to the chelating DME ligand both atoms gain coordination number 4 {Li? Bi 292(3); Bi? Si 263.3(14) pm; Bi? Li? Bi 132(1); Li? Bi? Li 148(1); φ(Li? Bi? Li? Bi) 83°}. In the case of dibismuthane 2 the centrosymmetric molecules are strung, their Bi-Bi groups forming nearly linear zigzag chains with shortened intermolecular contact distances {Bi-Bi 303.5(3); Bi …? Bi 380.4(3); Bi? Si 268 pm; Bi? Bi …? Bi 169; Bi? Bi? Si 97.4(5) and 92.0(5)°}. Structure and properties of 2 are compared with those of similar compounds; the crystal structure of brown, green metallic lustrous bis(4-methoxyphenyl)ditellane 5 already published by Ludlow and McCarthy[3] is reinvestigated with respect to very short intermolecular Te…?Te contacts. 相似文献
218.
Virginia Lea Miller Wei-li Lee Nai-Phuan Ong 《Journal of solid state chemistry》2005,178(5):1508-1512
We report the synthesis and elementary properties of the Co7Se8−xSx (x=0-8) and Ni7Se8−xSx (x=0-7) solid solutions. Both systems form a NiAs-type structure with metal vacancies. In general, the lattice parameters decrease with increasing x, but in the Ni7Se8−xSx system c increases on going from x=5 to 7. Magnetic susceptibility measurements show that all samples exhibit temperature-independent paramagnetism from 25-250 K. Samples within the Co7Se8−xSx system, as well as Ni7Se8 and Ni7SeS7, were found to be poor metals with resistivities of ∼0.20 and ∼0.06 mΩ cm at 300 K, respectively. The Sommerfeld constant (γ) was determined from specific heat measurements to be ∼13 mJ/molCoK2 and ∼7 mJ/molNiK2 for Co7Se8−xSx and Ni7Se8−xSx, respectively. 相似文献
219.
Attila Szorcsik Andrea Deák Zoltán A. Fekete Claudia Pellerito 《Journal of organometallic chemistry》2004,689(17):2762-2769
Nine complexes of tBu2Sn(IV)2+ were obtained in the solid state with ligands containing -COOH group(s) and aromatic {N} donor atom. The binding sites of the ligands were identified by FT-IR spectroscopic measurements. It was found that in most cases the -COO− groups are co-ordinated in monodentate manner. Nevertheless, in some of our complexes, the -COO− group forms bridges between two central {Sn} atoms resulting in the formation of an oligomeric structure, a motif that is characteristic only to the nicotinate compound. These pieces of information and the rationalisation of the experimental 119Sn Mössbauer nuclear quadrupole splittings, Δ, - according to the point charge model formalism - support the formation of octahedral (Oh) or trigonal bipyramidal (TBP) molecular structures. The X-ray diffraction analysis of one complex obtained as single crystal revealed the distortion of the TBP geometry towards square pyramidal (SP) one. This was rationalised by PM3 molecular modelling of the tBu2Sn(pdc) complex. In the asymmetric unit, the two chemically similar but symmetry independent molecules form pseudo-dimers, in which the Sn?Sn separation amounts to ca. 6.4 Å. The crystal lattice is stabilised by C-H?O hydrogen bonding between individual molecules. 相似文献
220.
Wilson Cunico Claudia R. B. Gomes Solange M. S. V. Wardell John N. Low Christopher Glidewell 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(7):o411-o414
rac‐2‐Isopropyl‐3‐(2‐nitrobenzyl)‐1,3‐thiadiazolin‐4‐one, C13H16N2O3S, is a rare example of a racemate crystallizing in the space group P212121, with one molecule each of S and R configurations, whose conformations are almost mirror images, within the asymmetric unit. The molecules of S configuration are linked by two C—H...O hydrogen bonds into a three‐dimensional framework, and the molecules of R configuration are linked by two further C—H...O hydrogen bonds into a different type of three‐dimensional framework; the two frameworks are linked by a fifth C—H...O hydrogen bond. 相似文献