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.     

Synthesis of 3-iodothiophenes via iodocyclization of (Z)-thiobutenynes

A simple synthesis of 3-iodothiophenes was demonstrated using a wide range of (Z)-thioenynes. The key step in the iodocyclofunctionalization was the selective reduction of the triple bond in (Z)-thioenynes by the addition of iodine as an electrophilic agent. The 3-iodothiophenes were obtained in good to excellent yields of 61–92%. The 3-iodothiophenes were used as substrates in Sonogashira cross-coupling reactions to obtain thiophene acetylenes.     

Removal efficiency of 75Se, 51Cr and 60Co from tidal water by mangrove sediments from Sepetiba Bay (SE Brazil)

Mangrove sediment cores sampled from Sepetiba Bay (SE Brazil) were covered with tidal water spiked with ⁷⁵Se, ⁵¹Cr and ⁶⁰Co to evaluate the removal efficiency of these radiotracers by underlying sediments. Variable time-evolution trends were observed along 115 h experiments, with significant differences between removal efficiencies of all radiotracers observed only after 70 h (⁵¹Cr > ⁶⁰Co > ⁷⁵Se). After an event of ⁶⁰Co release back to overlying water, there was a general trend of lower ⁶⁰Co removal than observed for other radiotracers during the period from 20 to 54 h. After this event, alternated periods of higher ⁶⁰Co and higher ⁷⁵Se removal trends were observed, attributed to behavioural differences expected for such anionic and cationic radiotracers. While ⁷⁵Se and ⁵¹Cr showed uniform time-evolution curves, as typically found in the literature for most radiotracers, ⁶⁰Co removal rates presented oscillations, probably due to sensitivity to changes in redox conditions within underlying sediments. Results evidenced the role of mangrove sediments as trace element sinks, which have implications for coastal water quality and for possible uses of such sediments in wastewater treatment systems.     

Ordering in spatially anisotropic triangular antiferromagnets

We investigate the phase diagram of the anisotropic spin-1/2 triangular lattice antiferromagnet, with interchain diagonal exchange J' much weaker than the intrachain exchange J. We find that fluctuations lead to a competition between (commensurate) collinear antiferromagnetic and (zigzag) dimer orders. Both states differ in symmetry from the spiral order known to occur for larger J', and are therefore separated by quantum phase transitions from it. The zero-field collinear antiferromagnet is succeeded in a magnetic field by magnetically ordered spin-density-wave and cone phases, before reaching the fully polarized state. Implications for the anisotropic triangular magnet Cs2CuCl4 are discussed.     

The potential energy surface of singlet cyclobutadiene and substituted analogs: a coupled-cluster study

Coupled-cluster investigations (CCSD/cc-pVDZ and CCSD/cc-pVQZ//CCSD/cc-pVDZ) of singlet cyclobutadiene and fifteen-substituted analogs were conducted. A local minimum with a square frame does not exist on their potential surfaces. The well-known rectangular D_2h minimum, the square D_4h transition state, and two additional stationary points were found on cyclobutadiene’s potential surface. This included a transition state with a rhombic carbon ring and C_2h symmetry, separating two equivalent puckered C_2v local minima. The predicted barriers were 19.7 and 19.8 kcal/mol at the CCSD/cc-pVDZ and CCSD/cc-pVQZ//CCSD/cc-pVDZ levels, respectively. The relative strain energies of rectangular D_2h cyclobutadiene and all fifteen-substituted analogs were obtained from isodesmic reactions. Progressive substitution with methyl or BH₂ groups continuously lowers ring strain while increasing substitution with fluorines or trifluoromethyl groups steadily increases ring strain. C₄(BH₂)₄ is 16.6 and 13.3 kcal/mol less strained than cyclobutadiene while C₄F₄ is 17.7 and 21.5 kcal/mol more strained at the levels above. Cyclobutadiene is more strained than both cyclopropene and cyclobutene by 12.2 and 37.0 kcal/mol, respectively. Electron density contours indicate that fluorine substitution raised the electron density especially in the short C=C ring bonds above/below the ring plane (π-electrons) but not in the ring plane (σ-electrons). BH₂-substitutions lower the ring π-electron density with little effect in the ring plane. Methyl substituents have little effect on electron densities. All rings retain a strong bond alternation tendency (rectangular) whether substituted with electron-donating or -attracting groups. One-bond coupling constants and the percent p-character in ring C-to-C and C-to-substituent bonds are described.     

Theory of particle transport phenomena during fatigue and time-dependent fracture of materials based on mesoscale dynamics and their practical applications

In this work, the mesoscale mechanics of metals, which links their microscopic physics and macroscopic mechanics, was established. For practical applications, the laws for quantitatively predicting life of cycle and time-dependent fracture behavior such as fatigue, hydrogen embrittlement, and high-temperature creep were derived using particle transport phenomena theories such as dislocation group dynamics, hydrogen diffusion, and vacancy diffusion. Furthermore, these concepts were also applied for estimating the degree of viscoelastic deterioration of blood vessel walls, which is dominated by a time-dependent mechanism, and for the diagnosis of aneurysm accompanied by the viscoelastic deterioration of the blood vessel wall. In these theories, new mechanical indexes were derived as dominant factors for predicting the life of fatigue crack growth and the time-dependent fracture of notched specimens of materials such as hydrogen embrittlement and high-temperature creep. Furthermore, as an example of a practical application, these theories were applied to estimate the degree of viscoelastic deterioration and chaotic motions of blood vessel walls, which are closely related to blood vessel diseases such as atherosclerosis and aneurysm. Moreover, new indexes to diagnose them were also proposed for clinical applications.     

A Classical Formulation of Quantum Theory?

We explore a particular way of reformulating quantum theory in classical terms, starting with phase space rather than Hilbert space, and with actual probability distributions rather than quasiprobabilities. The classical picture we start with is epistemically restricted, in the spirit of a model introduced by Spekkens. We obtain quantum theory only by combining a collection of restricted classical pictures. Our main challenge in this paper is to find a simple way of characterizing the allowed sets of classical pictures. We present one promising approach to this problem and show how it works out for the case of a single qubit.     

Recasting the (Synchrosqueezed) Short-Time Fourier Transform as an Instantaneous Spectrum

In a previous work, we proposed a time-frequency analysis called instantaneous spectral analysis (ISA), which generalizes the notion of the Fourier spectrum and in which instantaneous frequency is utilized to the fullest extent. In this paper, we recast both the Fourier transform (FT) and filterbank (FB) interpretations of the short-time Fourier transform (STFT) as instantaneous spectra. We show that to recast the FB interpretation of STFT as an instantaneous spectrum with valid structure, frequency reassignment is a fundamental necessity, thus demonstrating that this IS is closely related to the synchrosqueezed STFT. This result provides a new theoretical motivation for the synchrosqueezed STFT. Finally, we illustrate through example the instantaneous spectra corresponding to the FT and FB interpretations of STFT using two closed-form examples.