114 research outputs found

    A Suzuki Coupling Based Route to 2,2'-Bis(2-indenyl)biphenyl Derivatives

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    Because of the promising performance in olefin polymerization of 2,2'-bis(2-indenyldiyl)biphenyl zirconium dichloride, we developed a new and broadly applicable route to 2,2'-bis(2-indenyl)biphenyl derivatives. Reaction of the known 2,2'-diiodobiphenyl with the new 2-indenyl boronic acid did not result in the desired 2,2'-bis(2-indenyl)biphenyl (10); instead an isomer thereof, (spiro-1,1-(2,2'-biphenyl)-2-(2-indenyl)indane), was obtained. It was found that compound 10 could be made via a palladium-catalyzed reaction of 2,2-biphenyldiboronic acid with 2-bromoindene under standard Suzuki reaction conditions. However, the yield of this reaction was low at low palladium catalyst loadings, due to a competitive hydrolysis reaction of 2,2-biphenyldiboronic acid. HTE techniques were used to find an economically viable protocol. Thus, use of the commercially available 1.0 molar solution of (n-Bu)4NOH in methanol with cosolvent toluene led to precipitation of the pure product in a fast and clean reaction, using only 0.7 mol % (0.35 mol % per C-C) of the expensive palladium catalyst.

    Oxalic acid hydrogenation to glycolic acid:heterogeneous catalysts screening

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    To meet our ambitions of a future circular economy and drastically reduce CO2 emissions, we need to make use of CO2 as a feedstock. Turning CO2 into monomers to produce sustainable plastics is an attractive option for this purpose. It can be achieved by electrochemical reduction of CO2 to formic acid derivatives, that can subsequently be converted into oxalic acid. Oxalic acid can be a monomer itself and it is a potential new platform chemical for material production, as useful monomers such as glycolic acid and ethylene glycol can be derived from it. Today the most common route from oxalic acid to glycolic acid requires multiple steps as it proceeds via oxalic acid di-esters as intermediates. In this work, we aim to avoid the extra reaction step of esterification. We explore the direct conversion of oxalic acid to glycolic acid in a two-step approach. In the first step, we define the ideal reaction conditions and test commercially available catalysts. We show that the reduction of oxalic acid can be performed at much lower temperatures and glycolic acid yields higher than those reported previously can be obtained. In the second step, we explore the design principles required for ideal catalysts which avoid the formation of acetic acid and ethylene glycol as side products. We show that ruthenium is the most active metal for the reaction and that carbon appears the most suitable support for these catalysts. By adding tin as a promotor, we could increase the selectivity and yield further whilst maintaining high activity of the resulting catalyst. This research lays the foundation for the efficient direct reduction of oxalic acid to glycolic acid and defines the design parameters for even better catalysts and the ideal process and conditions.</p

    Condensation and interaction range in harmonic boson traps: a variational approach

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    For a gas of N bosons interacting through a two-body Morse potential a variational bound of the free energy of a confined system is obtained. The calculation method is based on the Feynman-Kac functional projected on the symmetric representation. Within the harmonic approximation a variational estimate of the effect of the interaction range on the existence of many-particle bound states, and on the N-T phase diagram is obtained.Comment: 14 pages+4 figures, submitted to phys.rev.

    Configural and featural processing in humans with congenital prosopagnosia.

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    Prosopagnosia describes the failure to recognize faces, a deficiency that can be devastating in social interactions. Cases of acquired prosopagnosia have often been described over the last century. In recent years, more and more cases of congenital prosopagnosia (CP) have been reported. In the present study we tried to determine possible cognitive characteristics of this impairment. We used scrambled and blurred images of faces, houses, and sugar bowls to separate featural processing strategies from configural processing strategies. This served to investigate whether congenital prosopagnosia results from process-specific deficiencies, or whether it is a face-specific impairment. Using a delayed matching paradigm, 6 individuals with CP and 6 matched healthy controls indicated whether an intact test stimulus was the same identity as a previously presented scrambled or blurred cue stimulus. Analyses of dÂŽ values indicated that congenital prosopagnosia is a face-specific deficit, but that this shortcoming is particularly pronounced for processing configural facial information
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