Phase Transfer Promoted Ruthenium Oxide Oxidations of Carbohydrates II

ABSTRACT

The use of a phase transfer catalyst, benzyltriethylammonium chloride (BTEAC), is described in conjunction with the ruthenium dioxide/periodate : water/chloroform system for the oxidation of carbohydrate alcohols to the corresponding ketone, aldehyde, or carboxylic acid. The method was found to be applicable to carbohydrates appropriately protected as acetals, ethers, or containing a benzoyloxy group not positioned to readily undergo β-elimination. While the method was very suitable for the oxidation of carbohydrate secondary alcohols to ketones, it was found to be less suitable for the oxidation of a carbohydrate primary alcohol to the corresponding aldehyde or carboxylic acid. Evidence presented suggests that under the mildly basic conditions of the reaction, ruthenium tetraoxide is converted to ruthenate and perruthenate ions in the aqueous solution and then the perruthenate ion is carried by the phase transfer catalyst into the organic layer where oxidation of the substrate occurs. A number of examples illustrating the scope of the method are presented.     

Direct Observation of the Binding Mode of the Phosphonate Anchor to Nanosized Polyoxotitanate Clusters

The structures of three newly synthesized phosphonate‐substituted polyoxotitanates are reported. The Ti/O core of [Ti₄O(OEt)₁₂(PhenylPO₃)] ( 1 ) is the building block for two larger phosphonate‐substituted nanoclusters, [Ti₂₅O₂₆(OEt)₃₆(PhenylPO₃)₆] ( 2 ) and [Ti₂₆O₂₆(OEt)₃₉(PhenylPO₃)₆]Br ( 3 ). All compounds exhibit a not previously recognized triply bridging binding mode of the phosphonate anchor with short connecting Ti? O bonds, the average of which is 2.010(7) Å. Comparison with previously reported work suggests that the binding mode of the phosphonate anchor is strongly dependent on the structure of the underlying substrate.     

Compactification of patterns by a singular convection or stress

A wide variety of propagating disturbances in physical systems are described by equations whose solutions lack a sharp propagating front. We demonstrate that presence of particular nonlinearities may induce such fronts. To exemplify this idea, we study both dissipative u_{t}+ partial differential_{x}f(u)=u_{xx} and dispersive u_{t}+ partial differential_{x}f(u)+u_{xxx}=0 patterns, and show that a weakly singular convection f(u)=-u;{alpha}+u;{m}, 0相似文献   

A computational investigation of 17O quadrupolar coupling parameters and structure in alpha-quartz phase GeO2

Ab initio band-structure calculations based on density functional theory have been completed for alpha-quartz phase GeO2 to obtain electric-field gradients (efg) for oxygen atoms, including those for GeO2 at elevated pressure and temperature. To interpret the resulting efg values and examine correlations between structure and 17O quadrupolar coupling parameters, additional ab initio self-consistent Hartree-Fock molecular orbital calculations were completed. The quadrupolar coupling constant was found to have a strong dependence on Ge-O distance and angleGe-O-Ge, with the quadrupolar asymmetry parameter being primarily dependent on angleGe-O-Ge. Analytical expressions describing these dependencies consistent with earlier investigations of analogous silicate compounds are also reported.     

Advances in ultra-high load polymer-supported peptide synthesis with phenolic supports: 2. Use of ‘hydrazinolysis-hplc’ to check for racemization on c-terminal amino acid loading and to determine peptide homogeneity during synthesis with selectively labile c-terminal anchoring linkages

2, 4-Dinitrophenyl-L-phenylalanine has been coupled to L-, D-, and DL-amino acid phenyl esters pendant upon a polymer matrix. The esters had been prepared by di-isopropylcarbodiimide-mediated condensation, catalyzed by 4-dimethylaminopyridine. Reverse phase high pressure liquid chromatography (HPLC), using elution solvents consisting of 10 vol.-% trifluoroacetic acid in water/acetonitrile mixtures, has been used to investigate the 2,4-dinitrophenyl L-L and L-D dipeptide mixtures obtained on hydrazinolysis of each of the dipeptide-matrix assemblies. ‘Hydrazinolysis-HPLC’ has been used also to determine intermediate peptide homogeneity in ultra-high load solid (gel) phase synthesis with Boc amino acids. Cross-linked poly(N-[2-(4-hydroxyphenyl)ethyl]acrylamide) and two derived polymers incorporating spacer groups have been used as supports. The spacer groups made possible peptide C-terminal attachment by either HF-labile benzyl ester or HF-labile cyclohexyl ester bonds, while still incorporating the phenolic ester linkage susceptible to rapid hydrazinolytic scission.     

Glass fragility and atomic ordering on the intermediate and extended range

The relation between the fragility of glass-forming systems, a parameter which describes many of their key physical characteristics, and atomic scale structure is investigated by using neutron diffraction to measure the topological and chemical ordering for germania, or GeO(2), which is an archetypal strong glass former. We find that the ordering for this and other tetrahedral network-forming glasses at distances greater than the nearest neighbor can be rationalized in terms of an interplay between the relative importance of two length scales. One of these is associated with an intermediate range, the other with an extended range and, with increasing glass fragility, it is the extended range ordering which dominates.     

两位物理学家的传说

很难想象,在物理学领域有比惠勒(John Archibald Wheeler)和费曼(Richard Feynman)这两位还要花样百出的心智组合。费曼于1939 年来到普林斯顿大学,希望在维格纳(Eugene Wigner)的指导下完成博士学业,然而到了那儿他才发现自己已经被分配给了惠勒,而那个家伙的年纪大他不到七岁。这两位极具创造力的思想家,彼此提点,相互协作,在他们的游戏中成功登顶。在《量子迷踪：费曼和惠勒如何玩转时间与实在》(The Quantum Labyrinth：How Richard Feynman and John Wheeler Revolutionized Time and Reality)这本书里,物理学家兼科学作家保罗·哈尔彭(Paul Halpern)详细描绘这对搭档的事业和关系。     

Approximate weinberg mixing

We present a model of the weak interactions in which a custodial symmetry that is not an invariance of the starting Lagrangian emerges in the effective low-energy sector of the theory. This symmetry maintains the relationM _w=M _z cos _w to all orders in the Higgs self-couplings to any required degree of accuracy, while leaving the quark mass spectrum completely unconstrained. The model is a local left-right symmetric chiral flavor gauge theory of the electroweak interactions in which the symmetry is spontaneously broken by fundamental Higgs fields which transform the same way under the chiral group as fermion Dirac and Majorana masses.