Production of New Carbon-Heteroatom Bonds Induced by Visible Light

[ES] En la presente tesis doctoral se describen metodologías novedosas, simples y rápidas con luz visible para producir compuestos con nuevos enlaces C-heteroátomo como C-B, C-P y C-S que representan estructuras valiosas en la síntesis orgánica moderna. La luz visible se emplea como fuente de energía más suave y sostenible que la tradicional (energía térmica). Por otro lado, también se han empleado nanorreactores espaciales como las redes de gel viscoelástico mediante enfoques 'ascendentes' para mejorar diferentes procesos en comparación con la disolución, en términos de cinética, selectividad o procesabilidad. Por lo tanto, el Capítulo 3 describe un procedimiento novedoso, directo y rápido para producir tiofenos que contienen boro empleando luz visible en disolución anaeróbica sin el uso de ningún fotocatalizador externo. Este estudio se ha ampliado a la borilación de haluros de heteroareno comerciales en condiciones aeróbicas en un nanorreactor de gel fácil de usar (Capítulo 4). La red de gel proporciona un microambiente estabilizador adecuado para soportar una amplia gama de sustratos, incluidos los ésteres de boronato de furano, tiofeno, selenofeno y de pirrol. El Capítulo 5 se centra en una nueva estrategia para lograr una fosforilación aeróbica eficiente de heteroarenos de cinco miembros mediante catálisis fotorredox dicromática en un nanorreactor basado en gel. La metodología, que opera mediante un mecanismo de transferencia de electrones fotoinducida consecutiva (ConPET), se ha aplicado con éxito a la síntesis sencilla y limpia de varios fosfonatos de heteroareno diferentes (furano, tiofeno, selenofeno, pirrol, oxazol o tioxazol), extendiéndose a la etapa tardía de la fosforilación del anticoagulante rivaroxabán. Por último, el Capítulo 6 muestra una tiolación (formación enlaces C-S) simple y efectiva, libre de metales, de haluros de heteroareno comerciales usando luz visible. Los resultados experimentales son consistentes con una reacción basada en un complejo aceptor-donador de electrones (EDA) entre una alquilamina y el haluro de heteroareno. El mecanismo del proceso se ha demostrado mediante estudios espectroscópicos, mientras que la robustez se ha demostrado mediante experimentos a escala de gramo y derivatización de última etapa.[CA] En la present tesi doctoral es descriuen metodologies noves, simples i ràpides amb llum visible per a produir compostos amb nous enllaços C-heteroàtom com C-B, C-P i C-S que representen estructures valuoses en la síntesi orgànica moderna. La llum visible s'utilitza com a font d'energia mes suau i sostenible que la tradicional (energia tèrmica). D'altra banda, també s'han emprat nanorreactors espacials com les xarxes de gel viscoelàstic mitjançant enfocaments 'ascendents' per a millorar diferents processos en comparació amb la dissolució, en termes de cinètica, selectivitat o procesabilitat. Per tant, el Capítol 3 descriu un procediment nou, directe i ràpid per a produir tiofens que contenen bor emprant llum visible en dissolució anaeròbica sense l'ús de cap fotocatalitzador extern. Aquest estudi s'ha ampliat a la borilació d'halurs d'heteroaré comercials en condicions aeròbiques en un nanorreactor de gel fàcil d'usar (Capítol 4). La xarxa de gel proporciona un microambient estabilitzador adequat per a suportar una àmplia gamma de substrats, inclosos els èsters de boronat de furan, tiofé, selenofé i de pirrol. El Capítol 5 se centra en una nova estratègia per a aconseguir una fosforilació aeròbica eficient de heteroarens de cinc membres mitjançant catàlisis fotorredox dicromàtica en un nanorreactor basat en gel. La metodologia, que opera mitjançant un mecanisme de transferència d'electrons fotoinducida consecutiva (ConPET), s'ha aplicat amb èxit a la síntesi senzilla i neta de diversos fosfonats d'heteroaré diferents (furan, tiofé, selenofé, pirrol, oxazol o tioxazol), estenent-se a l'etapa tardana de la fosforilació de l'anticoagulant rivaroxabán. Finalment, el Capítol 6 mostra una tiolació (formació d'enllaços C-S) simple i efectiva, lliure de metalls, d'halurs d'heteroaré comercials usant llum visible. Els resultats experimentals són consistents amb una reacció basada en un complex acceptor-donador d'electrons (EDA) entre una alquilamina i l'halur d'heteroaré. El mecanisme del procés s'ha demostrat mitjançant estudis espectroscòpics, mentre que la robustesa s'ha demostrat mitjançant experiments a escala de gram i derivatització d'última etapa.[EN] This thesis doctoral describes novel, simple, and rapid methodologies using visible light to produce compounds with new C-heteroatom bonds such as C-B, C-P and C-S that represent valuable scaffolds in modern organic synthesis. The employment of visible light as energy source highlights the concepts of green and sustainable chemistry considering its mild, safe, and eco-friendly advantages. On the other hand, spatially nanoreactors such as viscoelastic gel networks by 'bottom-up' approaches to improve different processes in comparison to solution, in terms of kinetics, selectivity or processability have been also developed. Thus, Chapter 3 describes a novel, straightforward, and fast procedure to produce boron-containing thiophenes employing visible light in anaerobic solution. Interestingly, the process does not require the use of any external photocatalyst. This study has been extended to the borylation of commercially available heteroarene halides under aerobic conditions in an easy-to-use gel nanoreactor (Chapter 4). The gel network provides an adequate stabilizing microenvironment to support wide substrate scope, including furan, thiophene, selenophene, and pyrrole boronate esters. Chapter 5 focus on a new strategy to achieve efficient aerobic phosphorylation of five-membered heteraroenes using dichromatic photoredox catalysis in a gel-based nanoreactor. The methodology, which operates by a consecutive photoinduced electron transfer (ConPET) mechanism, has been successfully applied to the straightforward and clean synthesis of a number of different heteroarene (furan, thiophene, selenophene, pyrrole, oxazole, or thioxazole) phosphonates, extending to the late-stage phosphonylation of the anticoagulant rivaroxaban. Lastly, regarding the construction of new C-S bonds, Chapter 6 shows a simple and effective metal-free thiolation of commercial heteroarene halides using visible light. The experimental results are consistent with the reaction taking place from an electron donor-acceptor (EDA) complex between an alkylamine and the heteroarene halide. Mechanistic aspects of the whole process have been demonstrated by spectroscopic measurements whereas the strength of this novel method has been proven by gram-scale experiment and late-stage derivatization.Herrera Luna, JC. (2022). Production of New Carbon-Heteroatom Bonds Induced by Visible Light [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/19105

Modelling the Product Development performance of Colombian Companies

Organised by: Cranfield UniversityThis paper presents the general model of the Product Development Process (PDP) in the Metal mechanics Industry in Barranquilla-Colombia, since this sector contributes significantly to the productivity of this industrial city. This case study counted on a five-company sample. The main goal was to model the current conditions of the PDP according to the Concurrent Engineering philosophy. The companies were selected according to their productive profile, in order to contrast differences regarding the structure of their productive processes, conformation of multidisciplinary teams, integration of different areas, customers and suppliers to the PDP; human resources, information, technology and marketing constraints.Mori Seiki – The Machine Tool Compan

DEVELOPMENT OF LAMBANOG (COCONUT VODKA) BASED CONCOCTION AS AUTHENTIC COCKTAIL DRINK IN THE PROVINCE OF THE PHILIPPINES

The purpose of the study is to develop Quezon’s authentic cocktail drink to promote the local product in Quezon Province using lambanog based and local ingredients in selected municipalities of 1st and 2nd districts in Quezon province specifically Mauban, Pagbilao, Sampaloc, Tayabas, Infanta, Sariaya and Lucena City. This is a Research and Development type of study which focuses on developing products that would contribute to the industry of the province. Owners, managers, and bartenders were the respondents of the study.   The methodology used in the study was Research and Development using a developed lambanog based concoction focused on three phases; generating phase where all  ingredients/materials for the development of local lambanog concoction were gathered, followed by the development phase where the concoction according to the acceptance of the taste and physical attributes of the lambanog cocktail were created and developed and lastly is the field try-out phase where the  acceptability of the lambanog based concoction to the market were tested. As to the result of the study, among the varieties of the different types of ingredients in Quezon province gathered by the researchers as modifiers,  the tanglad, butterfly dried ternate, bignay, mulberry fruit, katmon, liputi, and passion fruit were proven to have a good blend with the lambanog concoction when it comes to its appearance, taste/flavor, and odor/smell. Among the three cocktail drinks Cocktail 2 with concoction of lambanog, bignay, mulberry fruit, katmon, liputi and simple syrup got the highest acceptance level when it comes to its appearance. While to its taste/flavor and smell/odor cocktail 1 with the concoction of lambanog, buko, tanglad, and butterfly dried ternate got the highest acceptance level.   For the study to be more beneficial to the community as well as the lambanog and hospitality industry, further study is recommended which will focus on the marketability of the lambanog cocktails to be participated by the business establishment owners, staff and customers. &nbsp

Permanence and change in building system design

Thesis (M.S.)--Massachusetts Institute of Technology, Dept. of Architecture, 1990.Includes bibliographical references (p. 225-228).The obsolescence of our constantly changing built environment is leading architects, now more than ever, towards designing for unknown future requirements. This condition has become manifest in the design of "High Tech" Buildings (HTBs), where providing an adequate response to building growth and change has become a major design requirement. Moreover, the importance of HTBs in the future will require them not only to provide for flexibility and variability but also for permanent and meaningful physical configurations. The failure of today's Architects and Engineers to respond in a systematic way to these requirements has produced a situation where HTBs are becoming obsolete faster due to their rigidity. The Support-Infill Approach to building design is hereto considered as a design philosophy intended for the provision of change while concurrently establishing meaningful permanent configurations in built environments. Consequently, in this context the term "Support" refers to the permanent framework intended to give general order and meaning to a building as well as allowing for the flexible and adaptable "Infill" The main purpose of this thesis is then to explore and develop design strategies within this approach that will respond to the specific conditions of HTBs. The research is structured in five parts. First, general information is presented regarding the notion of buildings as systems. The second pan describes the nature and main characteristics of HTBs including the evolution of the concept and its relation to the problem of obsolescence. Thirdly, the problem of change and growth in buildings is depicted and design strategies for flexibility are explained. In Pan Four an exposition of the importance of permanence in the built environment is attempted and pertinent design strategies are presented in light of the work of contemporary architects. Finally the Support Infill approach is described as a framework for the implementation of design strategies intended for the achievement of more permanent and flexible environments. In addition, an appendix is provided which includes an adaptation of the S.A.R. methodology for Support design to the case of HTBs.by Pablo Luna Herrera.M.S