Syntheses of Functionalized Benzylic Compounds: Development of Palladium-Catalyzed Decarboxylative Benzylation Reactions

Carbon-carbon bond formation between the benzyl carbon and a functional group is important in organic synthesis because majority of the compounds in the chemical literature contain aromatic cores appended with different functionalities in the benzyl carbon. These compounds are utilized in pharmaceuticals and medicinal chemistry. While current literature in Pd-catalyzed benzylations is increasingly becoming recognized, conventional methodologies require the use of toxic benzyl halides, stoichiometric bases and/or performed organometallics which not only generate benzyl compounds but also give side products and toxic metal wastes. Our research group has a long-standing interest using decarboxylation as a tool in constructing diverse compounds without the need of base and preformed organometallics. Previously applied in the synthesis of functionalized allylic compounds from allyl esters, we envisioned to utilize this tool towards the synthesis of functionalized benzylic compounds from benzyl esters. We thought that it would be feasible and ideal to perform decarboxylative benzylation (DcB) based from well-explored decarboxylative allylation (DcA) methodology. Indeed, we were able to show that Pd-catalyzed DcB was an indispensable tool in synthesizing functionalized benzylic compounds in good to high yields. This was shown in the syntheses of benzyl ketones and benzyl alkynes. In the DcB of ketones, simple and benzo-fused β-ketoesters underwent decarboxylation affording benzyl ketones in good to high yields. DcB was also regiospecific, the kinetically preformed enolate did not undergo thermodynamic isomerization resulting to direct functionalization to the carbon next to the carboxylate group where it was once located. In addition to naphthyl and simple benzyls, heteroaromatics were also used as coupling partners with enolate. The nature of substituents in the ring and its position from the benzyl moiety affected benzylation. Depending on the nature of heterocycle, regioselective benzylation occurred resulting in formation of C-benzylation ketone, C-arylation ketone, or O-benzylation enol ether. The utility of DcB methodology was also used towards the synthesis of Nabumetone. In the DcB of alkynes, simple and benzo-fused propiolates underwent decarboxylation to generate benzyl alkynes in good to high yields. The use of biphenyl derived ligand was crucial in the synthesis of simple benzyl alkynes. The benzylic carbon in diaryls and heterocycles can also be used as coupling partners with alkynes

Identidad profesional y conocimiento matemático para la enseñanza de maestros en formación

En este estudio se pretende obtener una mayor comprensión sobre la identidad profesional en formación de estudiantes para maestro y las implicaciones para los programas de formación del profesorado. Se indaga sobre las reflexiones realizadas por estudiantes para maestro de educación primaria concernientes a sus experiencias relativas a la enseñanza y aprendizaje de las matemáticas y a conocimientos que estiman necesarios para enseñar matemáticas. Los resultados obtenidos revelan los aspectos que estos estudiantes destacan como elementos constitutivos de la identidad profesional del maestro haciendo mención a los componentes propios del proceso de enseñanza y aprendizaje de las matemáticas. Se propone una aproximación de la caracterización de la identidad profesional a través del conocimiento matemático para la enseñanza

A Bendixson-Dulac theorem for some piecewise systems

The Bendixson-Dulac Theorem provides a criterion to find upper bounds for the number of limit cycles in analytic differential systems. We extend this classical result to some classes of piecewise differential systems. We apply it to three different Liénard piecewise differential systems ¨ x+f±(x)˙ x+x = 0. The first is linear, the second is rational and the last corresponds to a particular extension of the cubic van der Pol oscillator. In all cases, the systems present regions in the parameter space with no limit cycles and others having at most one

Effect of different 3’ flanking regions on the activity of the Vitis vinifera alcohol dehydrogenase 2 promoter

3’untranslated regions (3' UTR) are isogene specific regions which contain sequences likely playing an important role in gene expression. To evaluate the importance of these regions on Vitis vinifera alcohol dehydrogenase 2 (VvAdh2) expression, we designed expression cassettes containing the luciferase reporter gene under the VvAdh2 or CaMV 35S promoters and flanked by different 3’ UTRs. Luciferase activity monitoring was performed through transient expression experiments, using biolistic on Cabernet Sauvignon suspension cells. Results showed that absence of the 3’ region had a strong down-regulating effect on the VvAdh2 promoter activity (but not on the CaMV 35S promoter activity). The nature of the flanking 3' UTR was shown to influence expression cassette activity. Whatever the promoter, VvAdh1 and VvAdh2 terminators had similar effect on expression of luciferase in air leading to an activity level very close to that of CaMV 35S terminator. Under anaerobiosis, luciferase expression was strongly increased with all terminators, VvAdh6 3'-end inducing the highest level of expression. Functional constructs with VvAdh2 promoter and VvAdh terminators designed in this study could be used wherever grapevine-homologous, stress-stimulated cassettes should be of interest

Determination of heat flows inside turbochargers by means of a one dimensional lumped model

In the present paper, a methodology to calculate the heat fluxes inside a turbocharger from diesel passenger car is presented. The heat transfer phenomenon is solved by using a one dimensional lumped model that takes into account both the heat fluxes between the different turbocharger elements, as well as the heat fluxes between the working fluids and the turbocharger elements. This heat transfer study is supported by the high temperature differences between the working fluids passing through a typical diesel turbocharger. These flows are the hot exhaust gases coming from the diesel engine exhaust passing through the turbine, the fresh air taken by the compressor, and the lubrication oil passing through the housing. The model has been updated to be used with a new generation of passenger car turbochargers using an extra element in the heat transfer phenomenon that is the water cooling circuit. This procedure allows separating the aerodynamic from the heat transfer effects, permitting to study the behavior of compressor and turbine in a separated way. (C) 2011 Elsevier Ltd. All rights reserved.Olmeda González, PC.; Dolz Ruiz, V.; Arnau Martínez, FJ.; Reyes Belmonte, MA. (2013). Determination of heat flows inside turbochargers by means of a one dimensional lumped model. Mathematical and Computer Modelling. 57(7-8):1847-1852. doi:10.1016/j.mcm.2011.11.078S18471852577-

Design, Analysis, and Applications of Iterative Methods for Solving Nonlinear Systems

In this chapter, we present an overview of some multipoint iterative methods for solving nonlinear systems obtained by using different techniques such as composition of known methods, weight function procedure, and pseudo-composition, etc. The dynamical study of these iterative schemes provides us valuable information about their stability and reliability. A numerical test on a specific problem coming from chemistry is performed to compare the described methods with classical ones and to confirm the theoretical results

Experiments on the influence of intake conditions on local instantaneous heat flux in reciprocating internal combustion engines

[EN] The present study tries to be a contribution for the development of more precise theoretical models for predicting the dissipation of heat through the combustion chamber walls of reciprocating (internal combustion) IC engines. A fast response thermocouple was embedded in the combustion chamber of a single cylinder engine to measure instantaneous wall temperatures. The heat flux was obtained by solving the one-dimensional transient energy equation with transient boundary conditions using the Fast Fourier Transform. The engine was tested under different operating conditions to evaluate the sensitivity of the measurement procedure to variations of three relevant combustion parameters: injection pressure, air temperature and oxygen concentration at the intake. The local heat flux obtained was compared with other relevant parameters that characterize the thermal behaviour of engines, showing, in most of the cases, correlation among them. The results showed that the instantaneous heat flux through the walls and hence the local wall temperatures are strongly affected by the ignition delay and the start of combustion. © 2010 Elsevier Ltd.Desantes, J.; Torregrosa, AJ.; Broatch, A.; Olmeda González, PC. (2011). Experiments on the influence of intake conditions on local instantaneous heat flux in reciprocating internal combustion engines. Energy. 36(1):60-69. doi:10.1016/j.energy.2010.11.011S606936

Numerical Estimation of Wiebe Function Parameters Using Artificial Neural Networks in SI Engine

[EN] In modeling an Internal Combustion Engine, the combustion sub-model plays a critical role in the overall simulation of the engine as it provides the Mass Fraction Burned (MFB). Analytically, the Heat Release Rate (HRR) can be obtained using the Wiebe function, which is nothing more than a mathematical formulation of the MFB. The mentioned function depends on the following four parameters: efficiency parameter, shape factor, crankshaft angle, and duration of the combustion. In this way, the Wiebe function can be adjusted to experimentally measured values of the mass fraction burned at various operating points using a least-squares regression, and thus obtaining specific values for the unknown parameters. Nevertheless, the main drawback of this approach is the requirement of testing the engine at a given engine load/speed condition. Furthermore, the main objective of this study is to propose a predictive model of the Wiebe parameters for any operating point of the tested SI engine. For this purpose, an Artificial Neural Network (ANN) is developed from the experimental data. A criterion was defined to choose the best-trained network. Finally, the Wiebe parameters are estimated with the neural networks for different operating conditions. Moreover, the mass fractions burned generated from the Wiebe functions are compared with the respective experimental values from several operating points measured in the engine test bench. Small differences were found between the estimated and experimental mass fractions burned. Therefore, the effectiveness of the developed ANN model as a prediction tool for the engine MFB is verified.Torregrosa, AJ.; Broatch, A.; Olmeda, P.; Aceros, S. (2021). Numerical Estimation of Wiebe Function Parameters Using Artificial Neural Networks in SI Engine. SAE International. 1-10. https://doi.org/10.4271/2021-01-037911

Experiments on subcooled flow boiling in I.C. engine-like conditions at low flow velocities

[EN] Subcooled boiling flow is specially attractive for engine cooling system design, as no essential changes in its architecture are required while it is still possible to take advantage of the highest rates of heat transfer associated with nucleate boiling, mostly at high engine loads. In this paper, experiments on subcooled boiling flow in representative temperature conditions were conducted with a usual engine coolant in the low velocity range, for which little information is available, even if it may be relevant when advanced thermal management strategies are used. The results were analyzed by comparison with a reference Chen-type model which provided reasonable results for relatively low wall temperatures, but with noticeable discrepancies at higher wall temperatures. Analysis of the deviations observed indicated a significant influence of the Prandtl number on the suppression factor, and the inclusion into the model of a first estimate of this effect produced a noticeable improvement in its results, thus suggesting that one such modified additive model may be useful for practical engine cooling applications. (C) 2013 Elsevier Inc. All rights reserved.This work has been supported by Ministerio de Ciencia e Innovacion through Grant TRA2010-16205. O. Cornejo is indebted to Senacyt Panama for their support.Torregrosa, AJ.; Broatch, A.; Olmeda, P.; Cornejo, O. (2014). Experiments on subcooled flow boiling in I.C. engine-like conditions at low flow velocities. Experimental Thermal and Fluid Science. 52:347-354. https://doi.org/10.1016/j.expthermflusci.2013.10.004S3473545

Assessment of the improvement of internal combustion engines cooling system using nanofluids and nanoencapsulated phase change materials

This is the author¿s version of a work that was accepted for publication in International Journal of Engine Research. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published as https://doi.org/10.1177/1468087420917494[EN] In recent years, due to the increasing need to reduce consumption of reciprocating internal combustion engines, new researches on different subsystems have raised. Among them, the use of nanofluids as a coolant medium seems to be an interesting alternative. In this work, the potential benefits of using nanofluids in the cooling system using an engine lumped model are studied. The methodology of the study starts with a whole description and validation of the model in both steady and transient conditions by means of a comparison with experimental results. Then, the potential benefits that could be obtained with the use of nanofluids are studied in a theoretical way. After that, the model is used to estimate the behavior of the system using different nanofluids in both stationary and transient conditions. The main results show that the advantages of using these new refrigerants are limited.The author(s) disclosed receipt of the following financial support for the research, authorship, and/or publication of this article: The equipment used in this work has been partially supported by FEDER project funds "Dotacion de infraestructuras cientifico tecnicas para el Centro Integral de Mejora Energetica y Medioambiental de Sistemas de Transporte (CiMeT)'' (grant number FEDER-ICTS-2012-06), framed in the operational program of unique scientific and technical infrastructure of the Spanish Government.Torregrosa, AJ.; Broatch, A.; Olmeda, P.; Dreif-Bennany, A. (2021). Assessment of the improvement of internal combustion engines cooling system using nanofluids and nanoencapsulated phase change materials. International Journal of Engine Research. 22(6):1939-1957. https://doi.org/10.1177/1468087420917494S1939195722