Oxidative dehydrogenation of crotonaldehyde overK2HPMo12O40catalyst

Summary The oxidative dehydrogenation of crotonaldehyde to furan and maleic anhydride was carried out over K₂HPMo₁₂O₄₀catalyst. A positive effect of water vapor on furan formation is explained by ability of the catalyst to isomerize 2E- to 2Z-crotonaldehyde.</o:p>     

An engine breaking the ΩEP-property

We present a construction which shows that some special continua do not have the nonwandering-eventually-periodic property. The construction applies e.g. to the topologist's sin curve and to the harmonic fan.     

Generalized double affine Hecke algebras of rank 1 and quantized del Pezzo surfaces

Let D be a simply laced Dynkin diagram of rank r whose affinization has the shape of a star (i.e., D₄,E₆,E₇,E₈). To such a diagram one can attach a group G whose generators correspond to the legs of the affinization, have orders equal to the leg lengths plus 1, and the product of the generators is 1. The group G is then a 2-dimensional crystallographic group: G=Z??Z², where ? is 2, 3, 4, and 6, respectively. In this paper, we define a flat deformation H(t,q) of the group algebra C[G] of this group, by replacing the relations saying that the generators have prescribed orders by their deformations, saying that the generators satisfy monic polynomial equations of these orders with arbitrary roots (which are deformation parameters). The algebra H(t,q) for D₄ is the Cherednik algebra of type C^∨C₁, which was studied by Noumi, Sahi, and Stokman, and controls Askey-Wilson polynomials. We prove that H(t,q) is the universal deformation of the twisted group algebra of G, and that this deformation is compatible with certain filtrations on C[G]. We also show that if q is a root of unity, then for generic t the algebra H(t,q) is an Azumaya algebra, and its center is the function algebra on an affine del Pezzo surface. For generic q, the spherical subalgebra eH(t,q)e provides a quantization of such surfaces. We also discuss connections of H(t,q) with preprojective algebras and Painlevé VI.     

On the interaction of silyl triflates with enamines: iminium ion formation versus silylation

The interaction of Me₃SiOTf and (C₆F₅)₃SiOTf with enamines generating α-silyl-substituted iminium ions is investigated. A trimethylsilyl iminium cation is formed as a long-lived species observable by NMR spectroscopy, whilst the tris(pentafluorophenyl)silyl analogue is very labile and prone to the loss of a proton. On the basis of the latter phenomenon, a method for the synthesis of β-silyl enamines is proposed.     

Tris(pentafluorophenyl)silyl enol ethers: synthesis and aldol reactions

Silyl enol ethers bearing three pentafluorophenyl groups at the silicon atom are described. These compounds undergo uncatalyzed aldol reactions with aliphatic, α,β-unsaturated, and aromatic aldehydes. The observed reactivity is analyzed in terms of the Lewis acidity of the silyl fragment.     

Effect of pressure on the proton transfer rate from a photoacid to a solvent. 4. Photoacids in methanol

The pressure dependence of the excited-state proton dissociation rate constant of four photoacids, 2-naphthol-6,8-disulfonate (2N68DS), 10-hydroxycamptothecin (10-CPT), 5-cyano-2-naphthol (5CN2), and 5,8-dicyano-2-naphthol (DCN2), are studied in methanol. The results are compared with the results of the pressure dependence study we recently conducted for several photoacids in water, ethanol, and propanol. The pressure dependence is explained using an approximate stepwise two-coordinate proton transfer model. The increase in rate, as a function of pressure, manifests a strong dependence of proton tunneling on the distance which decreases with an increase of pressure between the two oxygen atoms involved in the process. The decrease in the proton transfer rate with increasing pressure reflects the dependence of the reaction on the solvent relaxation rate. We found that, for the relatively weak photoacids 2N68DS, 10-CPT, and 5CN2, the proton transfer rate constant increases by a factor of about 5-8 at a pressure of about 1.5 GPa. For a strong photoacid like DCN2, the rate increase was only by a factor of 2.