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991.
The complex cis,trans,cis-[PtCl(2)(OAc)(2)NH(3)(c-C(6)H(11)NH(2))] (JM-216) is currently undergoing clinical evaluation as an antitumor agent. In support of characterization and analysis of this complex a study of its isomers and other complexes [PtCl(m)()(OAc)((4)(-)(m)()())NH(3)(c-C(6)H(11)NH(2))] (m = 0-4) has been undertaken. The complexes have been obtained by a variety of synthetic routes which now extend the scope for the preparation of platinum(IV) antitumor complexes. As platinum(IV) complexes are very stable to substitution in the absence of catalysis, use has been made of both light and base catalysis to promote substitution. Oxidative addition to platinum(II) using hypervalent iodine reagents has also been used. The stereochemistry of the complexes has been confirmed by spectroscopic studies, primarily NMR including natural abundance (15)N NMR spectroscopy. 相似文献
992.
Brian Mckittrick Amedeo Failli Robert J. Steffan Richard M. Soll Philip Hughes Jean Schmid Andre A. Asselin C. C. Shaw R. Noureldin G. Gavin 《Journal of heterocyclic chemistry》1990,27(7):2151-2163
Three practical synthetic entries of functionalized 6-fluoro-7-substituted indole derivatives were developed in connection with the preparation of 7-fluoro-8-substituted-1,3,4,9-tetrahydropyrano[3,4-b]indole-1-acetic acid derivatives 11 . The first route, which permits group modification about position 8 of the pyranoindole skeleton, employs 2-bromo-3-fluoroaniline ( 18 ) as a key intermediate, the preparation of which was achieved by either a novel ortho metalation of 15 or via the intermediacy of 22 . The second route utilizes 32 to append a terminally functionalized three carbon side chain onto the indole template and in addition leads to 43 from 40 . The third route to the 7-fluoro-8-substituted-pyranoindole skeleton complements route two in that the synthetic pathway exploits 32 in a nucleophilic fashion to construct a terminally functionalized two carbon appendage onto the indole nucleus. 相似文献
993.
Vijay M. Krishnamurthy Dr. Brooks R. Bohall Chu‐Young Kim Dr. Demetri T. Moustakas Dr. David W. Christianson Prof. Dr. George M. Whitesides Prof. Dr. 《化学:亚洲杂志》2007,2(1):94-105
This paper describes a calorimetric study of the association of a series of seven fluorinated benzenesulfonamide ligands (C6HnF5?nSO2NH2) with bovine carbonic anhydrase II (BCA). Quantitative structure–activity relationships between the free energy, enthalpy, and entropy of binding and pKa and log P of the ligands allowed the evaluation of the thermodynamic parameters in terms of the two independent effects of fluorination on the ligand: its electrostatic potential and its hydrophobicity. The parameters were partitioned to the three different structural interactions between the ligand and BCA: the ZnII cofactor–sulfonamide bond (≈65 % of the free energy of binding), the hydrogen bonds between the ligand and BCA (≈10 %), and the contacts between the phenyl ring of the ligand and BCA (≈25 %). Calorimetry revealed that all of the ligands studied bind in a 1:1 stoichiometry with BCA; this result was confirmed by 19F NMR spectroscopy and X‐ray crystallography (for complexes with human carbonic anhydrase II). 相似文献
994.
Wen Lu Qin‐Yu Zhu Yong Zhang Xiao‐Min Lin Jie Dai 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(11):m496-m498
The title salt, bis[2,3‐bis(aminocarbonyl)‐8,9‐bis(methylsulfanyl)tetrathiafulvalenium] di‐μ‐bromido‐bis[bromidocopper(II)], (C10H10N2O2S6)2[Cu2Br4], contains 2,3‐bis(aminocarbonyl)‐8,9‐bis(methylsulfanyl)tetrathiafulvalenium radical cations, [DMT‐TTF(CONH2)2]·+, and [Cu2Br4]2− anions. The cations are associated across centres of inversion in a head‐to‐tail fashion via short face‐to‐face S...S stacking (TTF moiety). These dimers are further assembled into a one‐dimensional chain structure via interdimer double S...S contacts involving the methylsulfanyl groups. The one‐dimensional chains give rise to a two‐dimensional structure through intermolecular double N—H...O hydrogen bonds involving the amide group. The [Cu2Br4]2− anions, which straddle centres of inversion, are located between the cation layers. Electron paramagnetic resonance measurements show a radical signal, indicating that the two TTF·+ radicals are not completely coupled in the dimer. 相似文献
995.
Fontaine P Goldmann M Muller P Fauré MC Konovalov O Krafft MP 《Journal of the American Chemical Society》2005,127(2):512-513
We report the first direct evidence for the formation of circular surface micelles (hemimicelles) on the surface of water. These highly monodisperse 30 nm hemimicelles, made from a semifluorinated alkane deposited as a Langmuir monolayer, form organized hexagonal arrays as determined by small-angle X-ray diffraction conducted directly on the water surface at grazing incidence. 相似文献
996.
Mann DL Ware GM Bonnin E Eitenmiller RR Barna E Christiansen S De Borde JL DeVries J Gilliland P Hemmer J Kalman A Konings E Levin D Salvati L Woollard D 《Journal of AOAC International》2005,88(1):30-37
A liquid chromatographic (LC) method was validated for the determination of total vitamin B6 in infant formula. Total vitamin B6 was quantified by converting the phosphorylated and free vitamers into pyridoxine. Pyridoxine was determined by ion pair reversed-phase LC with fluorescence detection. The method was subjected to an AOAC collaborative study involving a factory-manufactured, milk- and soy-based infant formula. Each was spiked at 3 concentrations in the range of 0-1 microg/g and sent as blind duplicate to participant laboratories. Nine laboratories returned valid data which were statistically analyzed for outliers and precision parameters. The repeatability relative standard deviation (RSD(r)) ranges were 2.0-4.0 and 3.5-5.9% for fortified milk- and soy-based formulas, respectively. The reproducibility relative standard deviation (RSD(R)) ranges were 8.2-8.4 and 6.7-11.2% for fortified milk- and soy-based formulas, respectively. HORRAT values ranged from 0.42 to 0.53, indicating that the precision of the method is acceptable. The mean RSD(r):RSD(R) values were 0.60 and 0.55 for milk- and soy-based formulas, respectively. As expected, RSDs for the unfortified samples were higher, but their HORRAT values (0.81 and 2.06) helped define a realistic limit of quantitation as 0.05 microg/g. Recovery data were quantitative and varied between 81.4 and 98.0% (mean = 89.8%) for each of 6 spiked materials. 相似文献
997.
Vibrational relaxation cross sections of the H(2)O(upsilon(2) = 1) bending mode by H(2) molecules are calculated on a recent high-accuracy ab initio potential-energy surface using quasiclassical trajectory calculations. The role of molecular rotation is investigated at a collisional energy of 3500 cm(-1) and it is shown that initial rotational excitation significantly enhances the total (rotationally summed) vibrational relaxation cross sections. A strong and complex dependence on the orientation of the water angular momentum is also observed, suggesting the key role played by the asymmetry of water. Despite the intrinsic limitations of classical mechanics, these exploratory results suggest that quantum approximations based on a complete decoupling of rotation and vibration, such as the widely used vibrational close-coupling (rotational) infinite-order-sudden method, would significantly underestimate rovibrationally inelastic cross sections. We also present some rationale for the absence of dynamical chaos in the scattering process. 相似文献
998.
The [2.2.2]hericene ( 6 ), a bicyclo[2.2.2]octane bearing three exocyclic s-cis-butadiene units has been prepared in eight steps from coumalic acid and maleic anhydride. The hexaene 6 adds successively three mol-equiv. of strong dienophiles such as ethylenetetracarbonitrile (TCE) and dimethyl acetylenedicarboxylate (DMAD) giving the corresponding monoadducts 17 and 20 (k1), bis-adducts 18 and 21 (k2) and tris-adducts 19 and 22 (k3), respectively. The rate constant ratio k1/k2 is small as in the case of the cycloadditions of 2,3,5,6-tetramethylidene-bicyclo [2.2.2]octane ( 3 ) giving the corresponding monoadducts 23 and 27 (k1) and bis-adducts 25 and 29 (k2) with TCE and DMAD, respectively. Constrastingly, the rate constant ratio k2/k3 is relatively large as the rate constant ratio k1/k2 of the Diels-Alder additions for 5,6,7,8-tetramethylidenebicyclo [2.2.2]oct-2-ene ( 4 ) giving the corresponding monoadducts 24 and 28 (k1) and bis-adducts 26 and 30 (k2). The following second-order rate constants (toluene, 25°) and activation parameters were obtained for the TCE additions: 3 +TCE→ 23 : k1 = 0.591±0.012 mol?1·l·s?1, ΔH≠=10.6±0.4 kcal/mol, and ΔS≠ = ?24.0±1.4 cal/mol·K (e.u.); 23 +TCE→ 25 : k2=0.034±0.0010 mol?1·l·s?1, ΔH≠ = 10.6±0.6 kcal/mol, and ΔS≠ = ?29.7±2.0 e.u.; 4 +TCE→ 26 : k1 = 0.172±0.035 mol?1·l·s?1, ΔH≠ 11.3±0.8 kcal/mol, and ΔS≠ = ?24.0±2.8 e.u.; 24 +TCE→ 26 : k2 = (6.1±0.2)·10?4 mol?1·l·s?1, ΔH≠ = 13.0±0.3 kcal/mol, and ΔS≠ = ?29.5±0.8 e.u.; 6 +TCE→ 17 : k1 = 0.136±0.002 mol?1·l·s?1, ΔH≠ = 11.3±0.2 kcal/mol, and ΔS≠ = ?24.5±0.8 e.u.; 17 +TCE→ 18 : k2 = 0.0156±0.0003 mol?1·l·s?1, ΔH≠ = 10.9±0.5 kcal/mol, and ΔS≠ = ?30.1 ± 1.5 e.u.; 18 +TCE→ 19 : k3=(5±0.2) · 10?5 mol?1 mol?1 ·l·s?1, ΔH≠ = 15±3 kcal/mol, and ΔS≠ = ?28 ± 8 e.u. The following rate constants were evaluated for the DMAD additions (CD2Cl2, 30°): 6 +DMAD→ 20 : k1 = (10±1)·10?4 mol?1 · l·s?1; 20 +DMAD→ 21 : k2 = (6.5±0.1) · 10?4 mol?1 ·l·?1; 21 +DMAD→ 22 : k3 = (1.0±0.1) · 10?4 mol?1 ·l·s?1. The reactions giving the barrelene derivatives 19, 22, 26 and 30 are slower than those leading to adducts that are not barrelenes. The former are estimated less exothermic than the latter. It is proposed that the Diels-Alder reactivity of exocyclic s-cis-butadienes grafted onto bicycle [2.2.1]heptanes and bicyclo [2.2.2]octanes that are modified by remote substitution of the bicyclic skeletons can be affected by changes inthe exothermicity of the cycloadditions, in agreement with the Dimroth and Bell-Evans-Polanyi principle. Force-field calculations (MMPI 1) of 3, 4, 6 and related exocyclic s-cis-butadienes as a moiety of bicyclo [2.2.2]octane suggested single minimum energy hypersurfaces for these systems (eclipsed conformations, planar dienes). Their flexibility decreases with the degree of unsaturation of the bicyclic skeleton. The effect of an endocyclic double bond is larger than that of an exocyclic diene moiety. 相似文献
999.
Pierre Braunstein 《Journal of organometallic chemistry》2004,689(24):3953-3967
In this account, we focus on results from our laboratory to illustrate recent developments in various fields of organometallic chemistry. Studies on hemilabile P,N donor ligands and on the ion-pair behaviour of cationic Pd(II) complexes have led to the full characterization of complexes with η1-allyl ligands. This still rare bonding mode for the allyl ligand in palladium chemistry allows facile insertion of CO into the Pd-C σ-bond, in contrast to the situation in related η3-allyl Pd(II) complexes. In order to develop new homogeneous catalysts for the selective dimerization and oligomerization of ethylene, a range of Ni(II) complexes have been prepared with new chelating P,N ligands where P represents a phosphine, phosphinite or phosphonite donor group and N a pyridine or oxazoline moiety. Finally, we shall examine bottom-up approaches to the formation of new nanomaterials of magnetic or catalytic interest by covalent anchoring of metal complexes and clusters into mesoporous materials using functional phosphine or alkyne ligands containing an alkoxysilyl group. 相似文献
1000.
Eduardo Corts Corts Rafael Sosa Mendoza Maximiliano Santibez Gutirrez Olivia Garca‐Mellado De Corts 《Journal of heterocyclic chemistry》2004,41(2):273-276
The preparation and spectral properties often novel methyl 5‐[(o‐, m‐, and p‐substituted)‐phenylthio]‐2‐benzimidazolecarbamates with possible pharmacological activity as antihelmintics is described; by condensation and cyclization between 5‐methylthioures sulfate chloroformic acid methyl ester and 3,4‐diaminophenyl‐substituted‐phenylthio ether dissolved in ethanol. The structures of all final products were corroborated by ir; 1H‐nmr, 13C‐nmr and ms. 相似文献