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Selected AbstractsAcrolein Diethyl Acetal: A Three-Carbon Homologating Reagent for the Synthesis of ,-Arylpropanoates and Cinnamaldehydes by Heck Reaction Catalyzed by a Kaiser Oxime Resin Derived PalladacycleEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 18 2008Emilio Alacid Abstract A polymer palladacycle derived from Kaiser oxime resin was used as a source of palladium(0) in the chemoselective Heck reaction of acrolein diethyl acetal with aryl halides under ligand-free conditions. The use of typical Heck conditions afforded 3-arylpropionic esters, and the process can be directed to the synthesis of cinnamaldehydes under Cacchi conditions. These processes take place with rather low loading of the catalyst, which can be recovered by simple filtration and reused for at least five runs without competitive dehalogenation. This is the first time that a supported palladium complex has been reused under Cacchi conditions. ICP-OES analyses of the Pd content of the crude products in both transformations indicated lower leaching for the esters than for the aldehydes in the range up to 0.08 ppm for the esters and 0.8 ppm for the aldehydes.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Direct Synthesis of Protected Arylacetaldehydes by Tetrakis(phosphane)palladium-Catalyzed Arylation of Ethyleneglycol Vinyl EtherEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 3 2006Isabelle Kondolff Abstract A range of aryl bromides undergo Heck reaction with ethylene glycol vinyl ether, in the presence of [PdCl(C3H5)]2/cis,cis,cis -1,2,3,4-tetrakis[(diphenylphosphanyl)methyl]cyclopentane as catalyst, to give regioselectively protected arylacetaldehydes in good yields. The ,-arylation products were obtained in with 93,100,% selectivity with electron-poor aryl bromides or heteroaryl bromides. Furthermore, this catalyst can be used at low loading, even for reactions with sterically hindered aryl bromides. The aryl vinyl ether intermediates undergo subsequent ketalisation to give the corresponding 2-benzyl-1,3-dioxolane derivatives.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Molecular-Level Dispersion of Graphene into Poly(vinyl alcohol) and Effective Reinforcement of their NanocompositesADVANCED FUNCTIONAL MATERIALS, Issue 14 2009Jiajie Liang Abstract Despite great recent progress with carbon nanotubes and other nanoscale fillers, the development of strong, durable, and cost-efficient multifunctional nanocomposite materials has yet to be achieved. The challenges are to achieve molecule-level dispersion and maximum interfacial interaction between the nanofiller and the matrix at low loading. Here, the preparation of poly(vinyl alcohol) (PVA) nanocomposites with graphene oxide (GO) using a simple water solution processing method is reported. Efficient load transfer is found between the nanofiller graphene and matrix PVA and the mechanical properties of the graphene-based nanocomposite with molecule-level dispersion are significantly improved. A 76% increase in tensile strength and a 62% improvement of Young's modulus are achieved by addition of only 0.7,wt% of GO. The experimentally determined Young's modulus is in excellent agreement with theoretical simulation. [source] Efficient dispersion of multi-walled carbon nanotubes by in situ polymerizationPOLYMER INTERNATIONAL, Issue 5 2007Nantao Hu Abstract Multi-walled carbon nanotube (MWNT)-reinforced polyimide nanocomposites were synthesized by in situ polymerization of monomers in the presence of acylated MWNTs. The acyl groups associated with the MWNTs participated in the reaction through the formation of amide bonds. This process enabled uniform dispersion of MWNT bundles in the polymer matrix. The resultant MWNT,polyimide nanocomposite films were optically transparent with significant mechanical enhancement at a very low loading (0.5 wt%). Evidence has been obtained for improved interactions between the nanotubes and the matrix polymer. Copyright © 2006 Society of Chemical Industry [source] Palladium-Catalyzed Cyclopropanation of Alkenyl Silanes by Diazoalkanes: Evidence for a Pd0 MechanismCHEMISTRY - A EUROPEAN JOURNAL, Issue 12 2009Guillaume Berthon-Gelloz Dr. Abstract Pd0does the trick! Alkenyl silanes are efficiently cyclopropanated by diazoalkanes at low Pd loadings (see scheme). Clear evidence for the involvement of a Pd0 resting state for this reaction is given. Alkenyl silanes are efficiently converted to the corresponding silyl cyclopropanes in the presence of a slight excess of diazomethane (2,4,equiv) and a low loading of Pd(OAc)2 (<0.5,mol,%). Diazoethane and diazobutane can also be employed and yield silyl cyclopropanes with diastereoselectivities of up to 10:1 for the trans isomer. When conducted on a 4,g scale, the reaction only required a catalyst loading of 5×10,3,mol,%, which corresponds to a turnover frequency of 40,000,h,1. Competition experiments revealed that vinyl silanes can be selectively cyclopropanated in the presence of an aliphatic terminal alkene and styrene. The complex [Pd02(DVTMS)3] (38, DVTMS=divinyltetramethyldisiloxane) proved to be an exceptionally active catalyst for the cyclopropanation reaction, giving complete conversion at ,35,°C in 1,min. Intermolecular and intramolecular competition experiments with DVTMS (36), both with Pd(OAc)2 and 38, provided strong evidence for a Pd0(alkenyl silane)3 resting state. Detailed density functional calculations on the reaction pathways for the cyclopropanation of trimethylvinylsilane and DVTMS by diazomethane with Pd0 corroborated the experimental observations. [source] Iron,Palladium Association in the Preparation of Indoles and One-Pot Synthesis of Bis(indolyl)methanesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 32 2007Vincent Terrasson Abstract Indoles were prepared by annulation of the parent alkynylanilines with the use of a new FeCl3,PdCl2 catalytic combination. High yields were obtained by using low loadings of the transition-metal complex (FeCl3,PdCl2: 2 and 1 mol-%, respectively). One-pot accesses to bis(indolyl)methanes and trisubstituted indoles through annulation/Friedel,Crafts alkylation and annulation/1,4-Michael addition sequences, in which FeCl3 acts both as a cooxidant and a Lewis acid are described.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Synthesis of Polysubstituted Alkenes by Heck Vinylation or Suzuki Cross-Coupling Reactions in the Presence of a Tetraphosphane,Palladium CatalystEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 6 2003Florian Berthiol Abstract Through the use of [PdCl(C3H5)]2/cis,cis,cis -1,2,3,4-tetrakis[(diphenylphosphanyl)methyl]cyclopentane as a catalyst, a range of vinyl bromides undergo Suzuki cross-couplings with arylboronic acids in good yields. Furthermore, the catalyst can be used at low loadings, even for reactions of sterically hindered substrates. Mediated by this catalyst, stilbene and 1,1-diphenylethylene undergo Heck reactions with aryl halides to give triarylethylene derivatives. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Tetrakis(trimethysilyl)hypophosphate P2O2(OTMS)4: Synthesis, reactivity and application as flame retardantHETEROATOM CHEMISTRY, Issue 7 2007Catherine Ruflin The preparation of tetrakis(trimethy- silyl)hypophosphate, P2O2(OTMS)4 (TMS = SiMe3), which is easily obtained from cheap starting materials, is reported. Reaction with protic substrates (H2O, alcohols) proceeds under stepwise cleavage of silylethers, ROTMS, and formation of hypophosphoric acid, P2O2(OH)4. Amines in the presence of molecular sieves lead to desilylation and formation of ammonium salts of the [P2O2(OTMS)2(O,)2] dianion. On cotton fabrics, P2O2(OTMS)4 hydrolyzes to give P2O2(OH)4 within about 1 h when exposed to air, and this compound acts as an efficient flame retardant (limiting oxygen index >26%) even at low loadings (P content <3%). © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:721,731, 2007; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20373 [source] Influence of a novel castor-oil-derived additive on the mechanical properties and oxygen diffusivity of polystyreneJOURNAL OF APPLIED POLYMER SCIENCE, Issue 3 2010Markus Klinger Abstract Mechanical properties, densities, and oxygen diffusion coefficients have been measured in polystyrene samples (PS) as a function of additive loading. The additive employed is based on castor oil, and is a desirable alternative to phthalates. Tensile strength measurements indicate the additive renders PS stronger at low loadings, i.e. it antiplasticizes the material. In contrast, the additive plasticizes PS at high loadings. Specific volumes and oxygen diffusion coefficients do not show this dual behavior. Rather, one observes a monotonic decrease in density and oxygen diffusivity with an increase in additive loading. This suggests that the larger segmental motions responsible for the macroscopic properties of the polymer are influenced by the additive in a different manner than the local motions and confined changes in free volume that govern the mobility of oxygen. These data indicate that antiplasticization cannot be predicted solely from diffusivity and density measurements and, vice versa, trends in diffusivity cannot be deduced from mechanical measurements alone. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source] | |||||||||||||