A Convenient Synthesis of N-Alkyl and N,N-Dialkyltrifluoroacetamides in a Solid-liquid Two-Phase System in the Presence of Phase-Transfer Catalysts

Trifluoroacetamide is easily monoalkylated in a K₂ CO₃-organic solvent solid-liquid two-phase system affording in good to excellent yields N-alkyltrifluoroacetamides. Under the same conditions, the latter, in turn, react with alkylating agents giving N, N-dialkyltrifluoroacetamides in high yields.     

Numerical simulation of a double-gate MOSFET with a subband model for semiconductors based on the maximum entropy principle

A nanoscale double-gate MOSFET is simulated with an energy-transport subband model for semiconductors formulated starting from the moment system derived from the Schr?dinger–Poisson–Boltzmann equations. The system is closed on the basis of the maximum entropy principle and includes scattering of electrons with acoustic and non-polar optical phonons. The proposed expression of the entropy combines quantum effects and semiclassical transport by weighting the contribution of each subband with the square modulus of the envelope functions arising from the Schr?dinger–Poisson subsystem. The simulations show that the model is able to capture the relevant confining and transport features and assess the robustness of the numerical scheme.     

Some trends in the theory of groups with finitely many normalizers

Ricerche di Matematica - This paper provides an account of results and methods from the theory of infinite groups admitting only finitely many normalizers of subgroups with a given property. Some...     

Screening of Three Transition Metal‐Mediated Reactions Compatible with DNA‐Encoded Chemical Libraries

The construction of DNA‐encoded chemical libraries (DECLs) crucially relies on the availability of chemical reactions, which are DNA‐compatible and which exhibit high conversion rates for a large number of diverse substrates. In this work, we present our optimization and validation procedures for three copper and palladium‐catalyzed reactions (Suzuki cross‐coupling, Sonogashira cross‐coupling, and copper(I)‐catalyzed alkyne‐azide cycloaddition (CuAAC)), which have been successfully used by our group for the construction of large encoded libraries.     

Synthesis and characterization of iPP‐sPP stereoblock produced by a binary metallocene system

Stereoblock polypropylenes comprising of iPP and sPP segments are synthesized by polymerization of the following binary system of metallocenes: the C_s‐symmetric [2,7‐t‐Bu₂(Flu)₂Ph₂C(Cp)ZrCl₂] and the C₂‐symmetric rac‐Me₂Si(2‐Me‐4‐Ph‐Ind)₂ZrCl₂. Blends of samples made either by each catalyst individually (solution blend) with materials obtained with the mixed catalyst system (reactor blend) are compared. The simultaneous presence of MAO and DEZ, enhancing fast and reversible transfer of the growing chains between the two active centers, leads to the formation of a stereoblock microstructure. In this case, low molecular weight polymers are obtained. The junction between the blocks is qualitatively observed in ¹³C NMR. When made in toluene, the stereoblock material consists of a majority of syndiotactic sequences, whereas the ratio is more equilibrated when the polymerization was conducted in the more polar chlorobenzene. This is confirmed by the results obtained with ¹³C NMR, CRYSTAF, HT HPLC, DSC, SSA, WAXD, and optical microscopy. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1422–1434     

Solvent‐free inkjet printing process for the fabrication of conductive,transparent, and flexible ionic liquid‐polymer gel structures

A new and solvent‐free process for the fabrication of inkjet printed ionic liquid‐polymer gel microstructures with high‐resolution (line widths of ～40 μm), good electrical conductivity (5–30 mS cm^?1), optical transparency, and mechanical flexibility is presented. Carrying out the printing and polymerization process in nitrogen atmosphere eliminates the inhibiting influence of oxygen and guarantees homogeneously gelled structures. Careful selection and combination of ionic liquids (ILs) and unsaturated monomers makes it possible to achieve low viscosities which are printable with commercially available inkjet printers and printheads without adding extra solvents. By using different types and amounts of ILs and monomers the resulting properties of the printed IL‐polymer gels can be controlled in terms of ionic conductivity, optical transmission, and mechanical flexibility. Higher conductivities are possible by using a bifunctional instead of a monofunctional monomer, which allows one to lower the amount of monomer without loss in mechanical strength. Cast samples make it possible to obtain data of transmission (～90% for 170‐μm thick films) and mechanical flexibility (E = 0.02–0.23 MPa) of bulk material. Comparing electrical conductivity of printed and cast samples, the higher values of printed samples indicate the conductivity enhancing influence of moisture absorbed from the surrounding atmosphere after the fabrication process. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Macrocyclic Polyethers as Enolate Activators in Homogeneous and Heterogeneous Systems

Abstract

The ability of macrocyclic polyethers to activate enolates has been studied in the alkylation of de-oxybenzoin (1) with butyl derivatives nBuY (Y = Br, I, OMes) catalyzed by crown ether PHDB18C6 (7) or cryptand [2.2.2,C10] (8) under phase-transfer catalysis (PTC) and homogeneous (chlorobenzene) conditions. The enolate reactivity is mainly determined by the ligand (cryptand > crown ether) and solvent (increasing with the polarity, in the order: toluene < chlorobenzene < 1,2dichlorobenzene). Regioselectivity of the reaction is also remarkably affected by ligand and alkylating agent.     

Exploring the Reactivity of a Frustrated Sn/P Lewis Pair: The Highly Selective Complexation of the cis-Azobenzene Photoisomer

The reactivity of the geminal frustrated Lewis pair (FLP) (F₅C₂)₃SnCH₂P(tBu)₂ ( 1 ) was explored by reacting it with a variety of small molecules (PhOCN, PhNCS, PhCCH, tBuCCH, H₃CC(O)CH=CH₂, Ph[C(O)]₂Ph, PhN=NPh and Me₃SiCHN₂), featuring polar or non-polar multiple bonds and/or represent α,β-unsaturated systems. While most adducts are formed readily, the binding of azobenzene requires UV-induced photoisomerization, which results in the highly selective complexation of cis-azobenzene. In the case of benzil, the reaction does not lead to the expected 1,2- or 1,4-addition products, but to the non-stereoselective (tBu)₂PCH₂-transfer to a prochiral keto function of benzil. All adducts of 1 were characterised by means of multinuclear NMR spectroscopy, elemental analyses and X-ray diffraction experiments.