One pot obtention of a tetrabutylammonium hydroxide solution for ironporphyrin-OH- interaction studies in organic solvents

In this work we report the obtention of a tetrabutylammonium hydroxide (TBAOH) solution in acetonitrile in a one pot process in order to study the interaction ironporphyrinOH- in non-aqueous systems. All the reactions were carried out under dry argon atmosphere to prevent the contamination of the solution with CO2, which leads to the formation of (TBA)2CO3.

One-pot enzymatic resolution/separation of enantiomers using green solvents

Dissertação para obtenção do Grau de Mestre em Biotecnologia

One-pot synthesis of alpha,beta-epoxy ketones by palladium-catalyzed epoxidation-oxidation of terminal allylic alcohols

Described herein is a one-pot synthesis of a,p-epoxy ketones using a palladium-catalyzed epoxidation-oxidation sequence. Functionalized terminal allylic alcohols are treated with m-CPBA Under mild reaction conditions to obtain the alpha,beta-epoxy ketones. The main benefit of this approach is that the epoxidation of the terminal double bond and the oxidation of the secondary alcohol occured in the same reaction under mild reactions and both electron-donating and electron-withdrawing functionalities are tolerated in the reaction sequence. (C) 2010 Elsevier Ltd. All rights reserved.

One-pot synthesis of mixed (Z)-1,2-bis(organylchalcogene)-1-alkenes precursors of the novel beta-organylthio vinyllithium intermediates

One-pot hydrochalcogenation of 1-phenylthioacetylenes using organylselenolate and organyltellurolate anions generated by the insertions of selenium and tellurium in n-organyl lithium produced (Z)-1,2-bis(organylchalcogene)-1-alkenes. The chemical reactivity of these mixed 1,2-bis(organylchalcogene)-1-alkenes was studied by Te/Li and Se/Li stereoretentive exchanges carried out with n-butyl lithium, furnishing the new intermediate species (Z)-beta-organylthio vinyllithium anions, which were trapped with aldehydes, to give the (Z)-3-hydroxy vinyl thioethers with total control of the regio- and stereochemistry. (c) 2010 Elsevier Ltd. All rights reserved.

A comparison between thin film solar cells made from co-evaporated CuIn1-xGaxSe2using a one-stage process versus a three-stage process

Until this day, the most efficient Cu(In,Ga)Se2 thin film solar cells have been prepared using a rather complex growth process often referred to as three-stage or multistage. This family of processes is mainly characterized by a first step deposited with only In, Ga and Se flux to form a first layer. Cu is added in a second step until the film becomes slightly Cu-rich, where-after the film is converted to its final Cu-poor composition by a third stage, again with no or very little addition of Cu. In this paper, a comparison between solar cells prepared with the three-stage process and a one-stage/in-line process with the same composition, thickness, and solar cell stack is made. The one-stage process is easier to be used in an industrial scale and do not have Cu-rich transitions. The samples were analyzed using glow discharge optical emission spectroscopy, scanning electron microscopy, X-ray diffraction, current–voltage-temperature, capacitance-voltage, external quantum efficiency, transmission/reflection, and photoluminescence. It was concluded that in spite of differences in the texturing, morphology and Ga gradient, the electrical performance of the two types of samples is quite similar as demonstrated by the similar J–V behavior, quantum spectral response, and the estimated recombination losses.

“One-pot” enzymatic conversion of CO2 to methanol

Dissertação para obtenção do Grau de Mestre em Biotecnologia

Bio and chemocatalysis for stereo and regioselective one-pot reaction applications

The development of cost efficient, selective and sustainable chemical processes for production of chiral building blocks is of great importance in synthetic and industrial organic chemistry. One way to reach these objectives is to carry out several reactions steps in one vessel at one time. Furthermore, when this kind of one-pot multi step reactions are catalyzed by heterogeneous chemo- and bio-catalysts, which can be separated from the reaction products by filtration, practical access to chiral small molecules for further utilization can be obtained. The initial reactions studied in this thesis are the two step dynamic kinetic resolution of rac-2-hydroxy-1-indanone and the regioselective hydrogenation of 1,2-indanedione. These reactions are then combined in a new heterogeneously catalyzed one-pot reaction sequence enabling simple recovery of the catalysts by filtration, facilitating simple reaction product isolation. Conclusively, the readily available 1,2-indanedione is by the presented one-pot sequence, utilizing heterogeneous enzyme and transition metal based catalysts, transferred with high regio- and stereoselectivity to a useful chiral vicinal hydroxyl ketone structure. Additional and complementary investigation of homogeneous half-sandwich ruthenium complexes for catalyzing the epimerization of chiral secondary alcohols of five natural products containing additional non-functionalized stereocenters was conducted. In principle, this kind of epimerization reactions of single stereocenters could be utilized for converting inexpensive starting materials, containing other stereogenic centers, into diastereomeric mixtures from which more valuable compounds can be isolated by traditional isolation techniques.

Diblock and Triblock Copolymers of Styrene and Acetoxymethylstyrene by One-Pot ATRP

We describe the synthesis of diblock and triblock copolymers by sequential atom transfer radical polymerization of styrene and acetoxymethylstyrene. Contrary to the usual block copolymerization involving isolation of the macroinitiator, a convenient one-pot procedure is developed. This is possible because of the preferential polymerization of acetoxymethylstyrene, even in the presence of residual styrene, as inferred from characterization of the intermediate polystyrenes and the block copolymers by size exclusion chromatography, 1H NMR, Fourier transform infrared spectroscopy, differential scanning calorimetry, and GPEC techniques. The latent acetoxy functionalities in these block copolymers are shown to be easily unmasked to OOH and OBr functionalities, with the potential for block ionomers and dense graft architectures.

Synthesis of dimethyl acetal of ketones: design of solid acid catalysts for one-pot acetalization reaction

The synthesis of dimethyl acetals of carbonyl compounds such as cyclohexanone, acetophenone, and benzophenone has successfully been carried out by the reaction between ketones and methanol using different solid acid catalysts. The strong influence of the textural properties of the catalysts such as acid amount and adsorption properties (surface area and pore volume) determine the catalytic activity. The molecular size of the reactants and products determine the acetalization ability of a particular ketone. The hydrophobicity of the various rare earth exchanged Mg–Y zeolites, K-10 montmorillonite clay, and cerium exchanged montmorillonite (which shows maximum activity) is more determinant than the number of active sites present on the catalyst. The optimum number of acidic sites as well as dehydrating ability of Ce3+-montmorillonite and K-10 montmorillonite clays and various rare earth exchanged Mg–Y zeolites seem to work well in shifting the equilibrium to the product side.

One-pot synthesis of multivalent arrays of mannose mono- and disaccharides

The synthesis of a selection of multivalent arrays of mannose mono- and disaccharides, that are of potential use as anti-infective agents against enterobacteria infections, is described. (C) 2003 Elsevier Ltd. All rights reserved.

One-pot synthesis and characterization of soluble poly(aryl ether-ketone)s having pendant carboxyl groups

Aromatic poly(ether-ketone)s having pendant carboxyl groups have been obtained by direct, one-pot, Friedel-Crafts copolycondensation of 4,4'-diphenoxybenzophenone with a mixture of terephthaloyl chloride (TC) and trimellitic anhydride acid chloride (TAAC), over a wide range of TAAC/TC molar ratios, in the presence of anhydrous aluminum chloride. The syntheses were performed as precipitation-polycondensations, and the polymers were obtained in particulate form. Besides globular particles of polymer, small quantities of elongated, needlelike particles were observed when the mole ratio TAAC/TC was less than 1. Use of X-ray microdiffraction with synchrotron radiation has revealed that the needlelike material consists of a cyclic compound containing 10 phenylene units, i.e., the crystals are of a [2 + 2] macrocyclic dimer. The polymers obtained are soluble in strong acids and in mixtures of methanesulfonic acid or trifluoroacetic acid with chlorinated hydrocarbons. The molecular structures of the polymers were confirmed by H-1 and C-13 NMR spectroscopy. Reaction of TAAC with 4,4'-diphenoxybenzophenone produced mainly meta-orientation of the resulting ketone linkages. The size of the polymer particles, their molecular weights, and the melting behavior of the products obtained depend on the TAAC/TC ratio used. Ortho-keto acid residues, formed during reaction of anhydride groups of TAAC with 4,4'-diphenoxybenzophenone, exhibit ring-chain tautomerism. A carboxyl-containing aromatic polyketone derived from p-terphenyl, and thus having with no ether linkages in the main chain, was prepared by analogous chemistry, and functional derivatives of carboxy-substituted polyketones were also obtained and characterized.

The molecular structure and one-pot synthesis of [Li(thf)3·Sn(SiMe3)3]

The molecular structure of [Li(thf)3 · Sn(SiMe3)3], prepared by a new, one-pot synthesis in 44% yield, has been determined by a single crystal X-ray diffraction study using synchrotron radiation and a CCD detector. The +Li(thf)3 and −Sn(SiMe3)3 moieties are joined by a Li–Sn bond, 2.865(5) Å in length. [Li(thf)3 · Sn(SiMe3)3] is isomorphous with its germanium analogue.

One-pot three component reaction involving cyclohexyl isocyanide for the synthesis of furo[3,4-b]chromenes

On stirring an equimolar mixture of 4-oxo-4H-chromene-3-carbaldehyde, ninhydrin and cyclohexyl isocyanide in CH(2)Cl(2)-MeOH (7: 1) at room temperature produces 3-cyclohexylimino-1-(2-hydroxy-1,3-dioxo-2,3-dihydro-1H-inden-2-yl)-1,3-dihydro-9H-furo[3,4-b]chromen-9-one which on hydrolysis produces 1-(2-hydroxy-1,3-dioxo-2,3-dihydro-1H-inden-2-yl)-1H-furo[3,4-b]chromene-3,9-dione. The structure of the latter compound was confirmed by single crystal X-ray diffraction