Síntesis y caracterización estructural de receptores iónicos con doble capacidad de complejación derivados de 2-amino-5-nitrosopirimidinas. Funcionalización de nanotubos de carbono con estos receptores
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2016-02-17
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Jaén: Universidad de Jaén
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[ES] Se persigue la síntesis de moléculas para funcionalizar superficies grafénicas. Esta funcionalización será llevada a cabo mediante funcionalización no covalente que consiste en la interacción π-π entre centros arénicos de una superficie grafénica y una base aromática de moléculas pequeñas previamente funcionalizadas.
Nuestras moléculas objetivo están constituidas por tres fragmentos conectados que tienen diferente función: 1) una unidad de anclaje a la superficie del carbón basada en un derivado de 2-amino-5-nitrosopirimidina; 2) una unidad funcional que son dos aminas del tris(2-aminoetil)amina (TREN) que mantiene las propiedades complejantes de iones metálicos que tenía antes de ser anclada a la superficie del carbón; 3) las dos unidades anteriores se encuentran conectadas a través de un separador alifático. Las moléculas de nuestro objetivo, tienen una unidad funcional basada en un fragmento de dietilentriamina, escogido por las buenas propiedades complejantes de algunos metales, como Pd y Pt.
La estrategia de síntesis va a consistir en la conexión de un fragmento de TREN a un derivado de 2-amino-5-nitrosopirimidina a través de una reacción de sustitución nucleofílica aromática efectuada por uno de los grupos amino del TREN. Para conseguir una monosustitución selectiva de la unidad de TREN se ha protegido una de sus aminas primarias con tritilo y las otras dos con tert-butoxicarbonilo (Boc) y a continuación se ha llevado a cabo la eliminación del tritilo y su separación del TREN-di-Boc. De esta manera obtenemos una amina libre capaz de unirse a la base de pirimidina.
Mediante esta estrategia hemos logrado un procedimiento de preparación de TREN-di-Boc que no necesita separaciones cromatográficas costosas y es escalable a preparaciones multigramo. Posteriormente hemos comprobado que este compuesto (TREN-di-Boc) es aplicable a la sustitución de grupos metoxilo en 2-amino-4,6-dimetoxi-5-nitrosopirimidina y que el producto de sustitución puede someterse a desprotección de Boc en medio ácido (con HBr acuoso) manteniendo la estructura de la nitrosopirimidina sin alterar.
En este TFG se ha conseguido sintetizar y caracterizar estructuralmente tres compuestos nuevos y se ha puesto a punto un procedimiento nuevo de desprotección de N-tritilo en presencia de grupos N-Boc.
[EN] The aim of this work is the synthesis of new molecules for the functionalization of graphene surfaces. This functionalization will take place through non-covalent functionalization that is based on the π-π interaction between arene centres of the graphene surfaces and aromatic rings of smalls molecules previously functionalized. Our objective molecules are formed by three fragments that possess different function: 1) a unit of anchorage to the carbon’s surface based in a derivate of 2-amino-5-nitrosopirimidine; 2) a functional unit that consist in two amines of the tris(2-aminoethil)amine (TREN) fragment which keep the metal complexing properties that it exhibited before being anchored at carbon’s surface; 3) the two previous units are connected through an aliphatic separator. The molecules of our objective have a functional unit based in fragments of diethilentriamine, and they have been chosen by the good complex properties towards some metals, like Pd and Pt, that it possesses. The synthesis strategy of these new molecules will involve the connection of a fragment of TREN to a derivate of 2-amine-5-nitrosopirimidine through an aromatic nucleophilic substitution reaction performed by an amine group of the TREN. To obtain a selective mono-substitution of TREN, it is firstly protected at one of its primary amines with a trityl group, and at the other two with tert-butoxycarbonyl (Boc) groups. Next, the elimination of the trityl graoup and his separation of the TREN-di-Boc has been performed. Thus, we obtained a free amine group able to bind to the pyrimidine base. Through this strategy we have set up a procedure for the preparation of TREN-di-Boc that doesn’t need expensive chromatography separations and it is scalable to multigram preparations. Later, we have verified that this compound (TREN-di-Boc) is applicable to the substitution of metoxy groups in 2-amino-4,6-dimethoxy-5-nitrosopirimidine and that the product of substitution can undergo deprotection of Boc group in acidic environment (with aqueous HBr) keeping the structure of the nitrosopirimidine unaltered. In this work, the synthesis of three new compounds and their full structural characterization has been achieved, and a new procedure of deprotection of N-trityl in the presence of N-Boc groups has been set up.
[EN] The aim of this work is the synthesis of new molecules for the functionalization of graphene surfaces. This functionalization will take place through non-covalent functionalization that is based on the π-π interaction between arene centres of the graphene surfaces and aromatic rings of smalls molecules previously functionalized. Our objective molecules are formed by three fragments that possess different function: 1) a unit of anchorage to the carbon’s surface based in a derivate of 2-amino-5-nitrosopirimidine; 2) a functional unit that consist in two amines of the tris(2-aminoethil)amine (TREN) fragment which keep the metal complexing properties that it exhibited before being anchored at carbon’s surface; 3) the two previous units are connected through an aliphatic separator. The molecules of our objective have a functional unit based in fragments of diethilentriamine, and they have been chosen by the good complex properties towards some metals, like Pd and Pt, that it possesses. The synthesis strategy of these new molecules will involve the connection of a fragment of TREN to a derivate of 2-amine-5-nitrosopirimidine through an aromatic nucleophilic substitution reaction performed by an amine group of the TREN. To obtain a selective mono-substitution of TREN, it is firstly protected at one of its primary amines with a trityl group, and at the other two with tert-butoxycarbonyl (Boc) groups. Next, the elimination of the trityl graoup and his separation of the TREN-di-Boc has been performed. Thus, we obtained a free amine group able to bind to the pyrimidine base. Through this strategy we have set up a procedure for the preparation of TREN-di-Boc that doesn’t need expensive chromatography separations and it is scalable to multigram preparations. Later, we have verified that this compound (TREN-di-Boc) is applicable to the substitution of metoxy groups in 2-amino-4,6-dimethoxy-5-nitrosopirimidine and that the product of substitution can undergo deprotection of Boc group in acidic environment (with aqueous HBr) keeping the structure of the nitrosopirimidine unaltered. In this work, the synthesis of three new compounds and their full structural characterization has been achieved, and a new procedure of deprotection of N-trityl in the presence of N-Boc groups has been set up.