Química comprehensiva de aminales macrocíclicos

ilustraciones

Autores:
Rivera Umaña, Augusto
Tipo de recurso:
Book
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2020
Institución:
Universidad Nacional de Colombia
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Universidad Nacional de Colombia
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spa
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oai:repositorio.unal.edu.co:unal/81290
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https://repositorio.unal.edu.co/
Palabra clave:
540 - Química y ciencias afines::547 - Química orgánica
Síntesis (Química orgánica)
Reacciones bioquímicas
Biosíntesis
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dc.title.spa.fl_str_mv Química comprehensiva de aminales macrocíclicos
title Química comprehensiva de aminales macrocíclicos
spellingShingle Química comprehensiva de aminales macrocíclicos
540 - Química y ciencias afines::547 - Química orgánica
Síntesis (Química orgánica)
Reacciones bioquímicas
Biosíntesis
title_short Química comprehensiva de aminales macrocíclicos
title_full Química comprehensiva de aminales macrocíclicos
title_fullStr Química comprehensiva de aminales macrocíclicos
title_full_unstemmed Química comprehensiva de aminales macrocíclicos
title_sort Química comprehensiva de aminales macrocíclicos
dc.creator.fl_str_mv Rivera Umaña, Augusto
dc.contributor.author.none.fl_str_mv Rivera Umaña, Augusto
dc.subject.ddc.spa.fl_str_mv 540 - Química y ciencias afines::547 - Química orgánica
topic 540 - Química y ciencias afines::547 - Química orgánica
Síntesis (Química orgánica)
Reacciones bioquímicas
Biosíntesis
dc.subject.lemb.none.fl_str_mv Síntesis (Química orgánica)
Reacciones bioquímicas
Biosíntesis
description ilustraciones
publishDate 2020
dc.date.issued.none.fl_str_mv 2020
dc.date.accessioned.none.fl_str_mv 2022-03-22T00:56:24Z
dc.date.available.none.fl_str_mv 2022-03-22T00:56:24Z
dc.type.spa.fl_str_mv Libro
dc.type.driver.spa.fl_str_mv info:eu-repo/semantics/book
dc.type.version.spa.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.coar.spa.fl_str_mv http://purl.org/coar/resource_type/c_2f33
dc.type.coarversion.spa.fl_str_mv http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.content.spa.fl_str_mv Text
format http://purl.org/coar/resource_type/c_2f33
status_str publishedVersion
dc.identifier.uri.none.fl_str_mv https://repositorio.unal.edu.co/handle/unal/81290
dc.identifier.instname.spa.fl_str_mv Universidad Nacional de Colombia
dc.identifier.reponame.spa.fl_str_mv Repositorio Institucional Universidad Nacional de Colombia
dc.identifier.repourl.spa.fl_str_mv https://repositorio.unal.edu.co/
url https://repositorio.unal.edu.co/handle/unal/81290
https://repositorio.unal.edu.co/
identifier_str_mv Universidad Nacional de Colombia
Repositorio Institucional Universidad Nacional de Colombia
dc.language.iso.spa.fl_str_mv spa
language spa
dc.relation.ispartofseries.none.fl_str_mv Colección textos;
dc.relation.references.spa.fl_str_mv Böhme H. α-Halogenierte amine und ihre umsetzungen. Angew. Chem-Ger. Edit. 1956; 68(6): 224.
Duhamel L. Chapter 20: Aminals. In: Patai S. Ed. The Chemistry of the Functional Groups, Supplement F: The Chemistry of amino, nitroso and nitro compounds and their derivatives. Part 2. Chichester: UK; John Wiley & Sons; 1982. p. 849 – 907.
Dickinson RG, Raymond AL. The crystal structure of hexamethylene- tetramine. J. Am. Chem. Soc. 1923; 45(1): 22 – 9.
Springborg J. Adamanzanes—bi-and tricyclic tetraamines and their coordination compounds. Dalton Trans. 2003; (9): 1653 - 65.
Springborg J, Pretzmann U, Olsen CE. An inert proton coordinated inside the tetrahedral cage [36]adamanzane. Synthesis of the inside monoprotonated amine 1,5,9,13-tetraazatricyclo[7.7.3.35,13] docosane. Acta Chem. Scand. 1995; (50): 294 – 8.
Springborg J, Pretzmann U, Olsen, C. E., Søtofte, I. Crystal structures of salts of mono- and triprotonated [36]adamanzane, 1,5,9,13-tetraazatricyclo[7.7.3.35,13]docosane, and equilibrium studies of the reactions between mono-, di- and triprotonated species, respectively, having none, one and two lone pairs pointing outwards. Acta Chem. Scand. 1998; (52): 289 – 95.
Pozharskii AF, Ozeryanskii VA, Filatova EA. Heterocyclic superbases: Retrospective and current trends. Chem. Heterocycl. Compd. 2012; 48(1): 200 – 19.
Ahabchane NH, Essassi EM, Bellan J, Lopez L, Lamandé L. Synthese de nouveaux macrocycle dérivés de la 1-pyrazolylbenzimidazole-2-thione. Phosphorus, Sulfur, Silicon Relat Elem. 2001; 173(1): 175 –92.
Alder RW, Sessions rbl. Chapter 18: Special properties of di- and poly- amines. In: Patai S. Ed. The Chemistry of the Functional Groups, Supplement F: The Chemistry of amino, nitroso and nitro compounds and their derivatives. Chichester: UK; John Wiley & Sons; 1982. p. 763 – 803.
Hoffmann R. Interaction of orbitals through space and through bonds. Acc. Chem. Res. 1971; 4(1): 1 – 9.
Dewar MJ, Dougherty RC. Capítulo 2. Teoría de las perturbaciones de los orbitales moleculares (pmo). En: Química Orgánica. Barcelona: España; Ed. Reverté S.A. 1980. p. 67 – 83.
Eliel EL. Conformational analysis in heterocyclic systems: Recent results and applications. Angew. Chem. Int. Ed. Engl. 1972; 11(9): 739 – 50.
Hutchins RO, Kopp LD, Eliel EL. Repulsion of syn-Axial electron pairs: The Rabbit-Ear Effect. J. Am. Chem. Soc. 1968; 90(25): 7174 – 5.
Lemieux RU, Pavia AA, Martin JC, Watanabe KA. Solvation effects on conformational equilibria: Studies related to the conformational properties of 2-methoxytetrahydropyran and related methyl glycopyranosides Can. J. Chem. 1969; 47(23): 4427 – 39.
Edward JT. Stability of glycosides to acid hydrolysis: A conformational analysis. Chem. Ind. 1955; (36): 1102 – 4.
Salzner U. Origin of the anomeric effect revisited. Theoretical conformation analysis of 2-hydroxypiperidine and 2-hydroxyhexahydropyrimidine. J. Org. Chem. 1995; 60(4): 986 – 95.
Takahashi O, Yamasaki K, Kohno Y, Ohtaki R, Ueda K, Suezawa H, Umezawad Y, Nishio M. The anomeric effect revisited. A possible role of the CH/n hydrogen bond. Carbohydr. Res. 2007; (342): 1202 – 9.
Wolfe S. The Gauche effect. Some stereochemical consequences of adjacent electron pairs and polar bonds. Acc. Chem. Res. 1972; 5(3): 102 – 11.
Dale J. Exploratory calculations of medium and large rings. Part 1. Conformational minima of cycloalkanes. Act Chem. Scand. 1973; 1(27): 1115 – 29.
Singh A, Ganguly B. Probing the influence of solvent effects on the conformational behavior of 1,3-diazacyclohexane systems. J. Phys. Chem. A. 2007; 111(39): 9884 – 9.
Schreiber SL. Target-oriented and diversity-oriented organic synthesis in drug discovery. Science. 2000; 287(5460): 1964 – 9.
Spandl RJ, Díaz‐Gavilán M, O’Connell KmG, Thomas GL, Spring DR. Diversity-oriented synthesis. Chem. Rec. 2008; 8(3): 129 – 142.
Butlerow A. Ueber ein neues Methylenderivat. Liebigs. Ann. Chem. 1860; 115(3): 322 – 7.
Jordan TH, Mak tcW. Molecular and crystal structure of hexamethylenetetramine triphenol. J. Chem. Phys. 1970; 52(7): 3790 – 4.
Duff JC. A new general method for the preparation of o-hydroxyaldehydes from phenols and hexamethylenetetramine. J. Chem. Soc. 1941; 547 – 50.
Duff JC. A new method for the preparation of p-dialkylaminobenzaldehydes. J. Chem. Soc. 1945; 276 – 7.
Sommelet M. Sur un mode de décomposition des halogénoalcoylates d’hexaméthylène-tétramine. CR Chim. 1913; (157): 852 – 3.
Delépine M. Hexamethylenetetramine compounds. CR Chim. 1895; (120): 743 – 5.
Delépine M. Preparation of primary amines. CR Chim. 1897; (124): 292 – 5.
Blaevi N, Kolbah D, Belin B, Šunji V, Kajfe F. Hexamethylene tetramine, A versatil reagent in organic synthesis. Synthesis. 1979; 1979(3): 161 – 76.
Kaur N, Kishore D. An insight into hexamethylenetetramine: a versatile reagent in organic synthesis. J. Iran. Chem. Soc. 2013; 10(6): 1193 – 228.
Galasso V. On the structure and spectroscopic properties of free and protonated adamanzanes. Chem. Phys. 2001; 270(1): 79 – 91.
Rivera A, González-Salas D, Ríos-Motta J, Hernández-Barragán A, Joseph-Nathan P. Preferred hydrogen bonding site of 1,3,6,8-tetraazatricyclo[4.3.1.13,8]undecane (tatu) to hydroquinone. J. Mol. Struct. 2007; 837(1-3): 142 – 6.
Rivera A, Moyano D, Maldonado M, Ríos-Motta J, Reyes-Velasco A. FT-IR and dFt studies of the proton affinity of small aminal cages. Spectrochim. Acta Part A Mol Biomol Spectrosc. 2009; 74(2): 588 – 90.
Rivera A, Núñez ME, Morales-Ríos MS, Joseph-Nathan P. Preparation of cage amine 1,3,6,8-tetraazatricyclo[4.3.1.13,8] undecane. Tetrahedron Lett. 2004; 45(41): 7563 – 5.
Rivera A, Núñez ME, Avella E, Ríos-Motta J. An Nmr study of sequential intermediates and collateral products in the conversion of 1,3,6,8-tetraazatricyclo[4.4.1.13,8]dodecane (tatd) to 1,3,6,8-tetraazatricyclo[4.3.1.13,8]undecane (tatu). Tetrahedron Lett. 2008; 49(13): 2154 – 8.
Bernal JS. Estudio de la reactividad química de 1,3,6,8-tetrazatriciclo [4.3.1.13,8]undecano (tatu), frente a electrófilos del tipo haluro de alquilo y nucleófilos duros y blandos [tesis doctoral]. Facultad de Ciencias, Universidad Nacional de Colombia; 2012.
Hernández MC. Reacción solvent-free de 1,3,6,8-tetrazatriciclo [4.3.1.13,8] undecano (tatu) con fenoles [tesis de maestría]. Facultad de Ciencias, Universidad Nacional de Colombia; 2007.
Rivera A, Rojas JJ, Osorio HJ, Ríos-Motta J, Bolte M. Crystal structure of the 1:2 co-crystal of 1,3,6,8-tetraazatricyclo[4.3.1.13,8]undecane (tatu) and 4-chlorophenol. Acta Crystallogr. E Crystallogr. Commun. 2016; 72(11): 1648 – 50.
Rivera A, Rojas JJ, Sadat-Bernal J, Ríos-Motta J, Bolte M. Mechanochemical synthesis and crystal structure of a 1:2 co-crystal of 1,3,6,8-tetraazatricyclo-[4.3.1.13,8]undecane (tatu) and 4-chloro-3,5- dimethylphenol. Acta Crystallogr. E Crystallogr. Commun. 2016; 72(11): 1651 – 3.
Rivera A, Osorio HJ, Uribe JM, Ríos-Motta J, Bolte M. Crystal structure of the 1,3,6,8-tetraazatricyclo[4.3.1.13,8]undecane (tatu)-4-nitrophenol (1/2) adduct: the role of anomeric effect in the formation of second hydrogen bond interaction. Acta Crystallogr. E Crystallogr. Commun. 2015; 71(11): 1356 – 60.
Bischoff CA. Studien über Verkettungen: XXXV. Formaldehyd und zweisäurige Basen. Ber. Dtsch. Chem. Ges. 1898; 31(3): 3248 – 58.
Rivera A, Ríos-Motta J. An unusual product obtained from condensation between ethylenediamine and formaldehyde in basic medium. Tetrahedron Lett. 2005; 46(30): 5001 - 4.
Murray-Rust P. Crystal and molecular structure of 1,3,6,8-tetraaza tricyclo[4.4.1.13,8]-dodecane, the 2 to 1 condensation product of formaldehyde and 1,2-diaminoethane, and the conformation of this system. J. Chem. Soc. Perkin 2. 1974; 10(0): 1136 – 41.
Rivera A, Ríos-Motta J, Bolte M. Redetermination of 1,3,6,8-tetraazatricyclo[4.4.1.13,8]dodecane. Acta Crystallogr. E Struct. Rep. on line 2014; 70(3): o266.
Rivera A, Gallo GI, Gayón ME, Joseph-Nathan P. A Novel Mannich type reaction using aminals in alkaline medium. Synth. Commun. 1993; 23(20): 2921 – 9.
Rivera A, Quevedo R. Solvent-free Mannich-type reaction of tetraazatricyclododecane (tatd) with phenols. Tetrahedron Lett. 2013; 54(11): 1416 – 20.
Rivera A, Nerio LS, Quevedo R. Synthesis of macrocyclic and linear benzylimidazolidine oligomers from solvent free aromatic Mannich-type reaction. Tetrahedron Lett. 2015; 56(44): 6059 – 62.
Rivera A, Ríos-Motta J, Quevedo R, Joseph-Nathan, P Nuevos aspectos de la reacción tipo Mannich en medio básico de 1,3,6,8-tetrazatriciclo[4.4.1.13,8] dodecano (tatd) con fenoles. Rev. Colomb. Quím. 2005; 34(2): 117 – 25.
Baldwin JE. Rules for Ring Closure. J. Chem. Soc., Chem. Comm. 1976; (18): 734 – 6.
Rivera A, Torres OL, Leitón JD, Morales-Ríos MS, Joseph-Nathan P. An efficient approach to 1,3,5-tris-arylhexahydro-1,3,5-triazines. Synth. Commun. 2002; 32(9): 1407 – 14.
Smith, M. B., March, J. March’s Advanced Organic Chemistry: Reactions, Mechanisms, and Structure. 6th Ed. Hoboken, New Jersey: usa, John Wiley & Sons, Inc., 2007. p. 798, 1054.
Pearson RG. Hard and Soft Acids and Bases. J. Am. Chem. Soc. 1963; 85(22): 3533 – 39.
Rivera A, Maldonado M, Núñez ME, Joseph-Nathan P. Nucleophilic substitution at the aminalic carbon of some macrocyclic polyaminals. Heterocycl. Commun. 2004; 10(1): 77 – 80.
Katritzky AR, Yang Z, Lam JN. Aminoalkylbenzotriazoles: Reagents for the Aminoalkylation of Electron Rich Heterocycles. Tetrahedron. 1992; 48(23): 4971 – 78.
Katritzky AR, Lang H, Lan X. A New Route to N-Substituted Heterocycles. Tetrahedron 1993; 49(14): 2829 – 38.
Rivera A, Quiroga D, Jiménez-Cruz L, Fejfarová K, Dušek, M. New cyclic aminals derived from rac-trans-1,2-diaminocyclohexane: synthesis and crystal structure of racemic 1,8,10,12-tetraazatetracyclo[8.3.1.18,12.02,7]pentadecane and a route to its enantiomerically pure (R,R) and (S,S) isomers. Tetrahedron Lett. 2012; 53(3): 345 – 8.
Osorio HJ. Estudio de la reactividad química de los aminales asimétricos (2R7R) y (2S,7S)-1,3,10,12-tetrazatetraciclo [8.3.1.18,12.02,7]pentadecano frente a nucleófilos [tesis doctoral]. Facultad de Ciencias, Universidad Nacional de Colombia; 2015.
Rivera A, Guevara-Pulido J, Sadat-Bernal J, Ríos-Motta J, Zaragoza G. Structure of the solid state 2:1 molecular of 1,5:3,7-dimethano-1,3,5,7- benzotetrazonine with hydroquinine. Acta Crystallogr. C. 2009; (65): o435 –7.
Kuznetsov A, Shukkur A, Kamara K. The synthesis of 1,5:3,7-dimethano 1,3,5,7-benzotetrazecine. Russ. Chem. Bull. 2007; 56(3): 563 – 5.
Murray-Rust P, Riddell FG. The stability and conformation of the 1,3,6,8-tetraazatricyclo[4.4.1.13,8]dodecane system: the structure of the condensation product of 1,2-diaminocyclohexane and formaldehyde. Can. J. Chem. 1975; 53(13): 1933 – 5.
Quiroga DE. Estudios de la reacción de los aminales quirales (2R,7R,11S,16S)- y (2S,7R,11S,16R)-1,8,10,17-tetrazapentaciclo [8.8.1.18,170.2,70.11,16]eicosano con nucleófilos y electrófilos [tesis doctoral]. Facultad de Ciencias, Universidad Nacional de Colombia; 2013.
Rivera A, Pacheco DJ, Ríos-Motta J. Pojarová M, Dušek M. 1,1’-[(2,3,3a,4,5,6,7,7a-Octahydro-1H-1,3-benzimidazole-1,3-diyl)bis (methylene)]-bis(1H-benzotriazole). Acta Crystallogr. E Struct Rep on line. 2011; 67(11): o3071.
Murray-Rust P, Smith I. 1,4-Dimethanodibenzo[d,i]-1,3,6,8-tetrazecine Acta Crystallogr. B. 1975; 1975(31): 587 – 9.
Volpp G. Zur Struktur einiger Kondensationsprodukte von Formaldehyd mit 1.2-Diaminen. Chem. Ber. 1962; 95(6): 1493 – 4.
Rivera A, Maldonado M. Unexpected behavior of 6H,13H-5:12,7:14- dimethanedibenzo[d,i][1,3,6,8]tetraazecine (dmdbta) toward phenols. Tetrahedron Lett. 2006; 47(42): 7467 – 71.
Duarte YA. Estudio de la reactividad química del bis aminal N,N ́-bis(1H- benzotriazol-1-il-metil)-1,2-diaminobenceno frente a fenoles. [tesis de maestría]. Facultad de Ciencias, Universidad Nacional de Colombia; 2009.
Menschutkin N. Beiträgen zur Kenntnis der Affinitätskoeffizienten der Alkylhaloide und der organischen Amine. Z. Phys. Chem. 1890; 1890(5): 589 – 600.
Menschutkin N. Über die Affinitätskoeffizienten der Alkylhaloide und der Amine. Z. Phys. Chem. 1890; 1890(6): 41 – 57.
Böhme H, Haake M. Über monoquartäre Salze aus Hexamethylenetetramin und α-halogenierten Aminen. Arch. Pharm. 1967; 300(8): 682 – 3.
Bachmann WE, Deno NC. The nitrosation of hexamethylene-tetramine and related compound. J. Am. Chem. Soc. 1951; 73(6): 2777 – 9.
Singer R, Vaughan K, Hooper DL. Open chain nitrogen compounds. Part XI. 3,7-bis(arylazo)-1,3,5,7-tetraazabicyclo[3,3,1]nonanes: The reaction of diazonium ions with ammonia-formaldehyde mixtures. Can. J. Chem. 1986; 64(8): 1567 – 72.
Vaughan K. Recent progress in the synthesis of bis-triazenes. Org. Preparat. Procedures Int. 2001; 33(1): 59 – 74.
Rivera A, Sadat-Bernal J, Ríos-Motta J, Dušek M, Palatinus L. Synthesis and structural studies of a new class of quaternary ammonium salts, which are derivatives of cage adamanzane type aminal 1, 3, 6, 8-tetraazatricyclo[4.3.1.13,8]undecane (tatu). Chem. Cent. J. 2011; 5(55): 1 – 8.
Rivera A, González-Salas D. Synthesis and characterization of novel triazenes from the reaction of the cyclic aminal 1,3,6,8-tetraazatricyclo[4.3.1.13,8] undecane (tatu) with diazonium ions. Tetrahedron Lett. 2010; 51(18): 2500 – 4.
Rivera A, Gallo GI, Joseph-Nathan P. Nitrosation of aminals: Preparation and characterization of 1,3-dinitrosoimidazolidine. Synth. Commun. 1997; 27(1): 163 – 8.
Peori MB, Vaughan K. Synthesis and characterization of novel bis-triazenes: 3,8-di[2-aryl-1-azenyl]-1,3,6,8-tetraazabicyclo[4.4.1] undecanes and 1,3-di- 2-[(4-methoxyphenyl)-1-diazenyl] imidazolidine. The reaction of diazonium ions with ethylenediamine/formaldehyde mixtures. J. Org. Chem. 1998; 63(21): 7437 – 44.
Maldonado M. Estudios químico del benzoaminal macrocíclico 6H,13H- 5,12:7,14-dimetanodibenzo[d.i][1,3,6,8]tetrazecina (dbta) [tesis doctoral]. Facultad de Ciencias, Universidad Nacional de Colombia; 2006.
Rivera A, Maldonado M, Ríos-Motta J. A Facile and Efficient Procedure for the Synthesis of New Benzimidazole-2-thione Derivates. Molecules. 2012; 17(7): 8578 – 86.
dc.rights.spa.fl_str_mv Universidad Nacional de Colombia, 2020
dc.rights.coar.fl_str_mv http://purl.org/coar/access_right/c_abf2
dc.rights.license.spa.fl_str_mv Atribución-NoComercial-SinDerivadas 4.0 Internacional
dc.rights.uri.spa.fl_str_mv http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.rights.accessrights.spa.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv Atribución-NoComercial-SinDerivadas 4.0 Internacional
Universidad Nacional de Colombia, 2020
http://creativecommons.org/licenses/by-nc-nd/4.0/
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eu_rights_str_mv openAccess
dc.format.extent.spa.fl_str_mv 70 páginas
dc.format.mimetype.spa.fl_str_mv application/pdf
dc.publisher.spa.fl_str_mv Universidad Nacional de Colombia. Facultad de Ciencias
dc.publisher.department.spa.fl_str_mv Sede Bogotá
dc.publisher.place.spa.fl_str_mv Bogotá, Colombia
institution Universidad Nacional de Colombia
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spelling Atribución-NoComercial-SinDerivadas 4.0 InternacionalUniversidad Nacional de Colombia, 2020http://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccesshttp://purl.org/coar/access_right/c_abf2Rivera Umaña, Augusto6b89a43ab51b5a9a07180bbbb12f4c1c6002022-03-22T00:56:24Z2022-03-22T00:56:24Z2020https://repositorio.unal.edu.co/handle/unal/81290Universidad Nacional de ColombiaRepositorio Institucional Universidad Nacional de Colombiahttps://repositorio.unal.edu.co/ilustracionesEste libro es una guía práctica sobre aminales cíclicos tipo caja o adamanza- nos, que examina exhaustivamente las reacciones características y las trans- formaciones, los métodos sintéticos y la eficiencia experimental. Es como una puerta de entrada para la investigación y el desarrollo en el campo de estas tetraminas tricíclicas que conforman la familia de los aminales caja, compuestos muy poco estudiados, algo incomprendidos y, muy interesan- tes, debido a sus propiedades químicas y a su uso promisorio en diversos campos de la química. (texto tomado de la fuente)A manera de prólogo -- Capítulo uno -- Consideraciones iniciales -- Principios, clasificación e historia -- Nomenclatura sistemática -- Nomenclatura simplificada de Springborg -- El papel de los electrones no compartidos de los nitrógenos -- Capítulo dos Consideraciones estructurales: relaciones 1,1- y 1,2-diamina y sus consecuencias -- Ambivalencia nucleo filicidad – electrofililicidad en los El efecto anomérico en los aminales caja -- Terminología para arreglos espaciales -- Capítulo tres -- Versatilidad sintética de los aminales cíclicos tipo caja -- Metodologías sintéticas usando aminales tipo caja -- Reaccionando como electrófilos frente a nucleófilos -- El 1,3,5,7-tetrazatriciclo[33113,7]decano 3 -- El 1,3,6,8-tetrazatriciclo[43113,8]undecano (TATU) 4 -- El 1,3,6,8-tetrazatriciclo[44113,8]dodecano (TATD) 5 -- Generalidades sobre las reglas de Baldwin -- El 1,8,10,12-tetrazatetraciclo[83118,1202,7] pentadecano (TATP) 6 -- El 1,5:3,7-dimetano-1,3,5,7-benzotetrazonina (benzoTATU) 7 -- El (2R,7R,11S,16S)-1,8,10,17 tetrazapentaciclo[88118,1702,70 11,16]eicosano (TAPE) 8 -- El 6H,13H-5,12:7,14-dimetanodibenzo[d,i][1,3,6,8]tetrazecina (DMDBTA) 9 -- Reaccionando como nucleófilos frente a electrófilos -- Bibliografíaprimera edición70 páginasapplication/pdfspaUniversidad Nacional de Colombia. Facultad de CienciasSede BogotáBogotá, ColombiaColección textos;Böhme H. α-Halogenierte amine und ihre umsetzungen. Angew. Chem-Ger. Edit. 1956; 68(6): 224.Duhamel L. Chapter 20: Aminals. In: Patai S. Ed. The Chemistry of the Functional Groups, Supplement F: The Chemistry of amino, nitroso and nitro compounds and their derivatives. Part 2. Chichester: UK; John Wiley & Sons; 1982. p. 849 – 907.Dickinson RG, Raymond AL. The crystal structure of hexamethylene- tetramine. J. Am. Chem. Soc. 1923; 45(1): 22 – 9.Springborg J. Adamanzanes—bi-and tricyclic tetraamines and their coordination compounds. Dalton Trans. 2003; (9): 1653 - 65.Springborg J, Pretzmann U, Olsen CE. An inert proton coordinated inside the tetrahedral cage [36]adamanzane. Synthesis of the inside monoprotonated amine 1,5,9,13-tetraazatricyclo[7.7.3.35,13] docosane. Acta Chem. Scand. 1995; (50): 294 – 8.Springborg J, Pretzmann U, Olsen, C. E., Søtofte, I. Crystal structures of salts of mono- and triprotonated [36]adamanzane, 1,5,9,13-tetraazatricyclo[7.7.3.35,13]docosane, and equilibrium studies of the reactions between mono-, di- and triprotonated species, respectively, having none, one and two lone pairs pointing outwards. Acta Chem. Scand. 1998; (52): 289 – 95.Pozharskii AF, Ozeryanskii VA, Filatova EA. Heterocyclic superbases: Retrospective and current trends. Chem. Heterocycl. Compd. 2012; 48(1): 200 – 19.Ahabchane NH, Essassi EM, Bellan J, Lopez L, Lamandé L. Synthese de nouveaux macrocycle dérivés de la 1-pyrazolylbenzimidazole-2-thione. Phosphorus, Sulfur, Silicon Relat Elem. 2001; 173(1): 175 –92.Alder RW, Sessions rbl. Chapter 18: Special properties of di- and poly- amines. In: Patai S. Ed. The Chemistry of the Functional Groups, Supplement F: The Chemistry of amino, nitroso and nitro compounds and their derivatives. Chichester: UK; John Wiley & Sons; 1982. p. 763 – 803.Hoffmann R. Interaction of orbitals through space and through bonds. Acc. Chem. Res. 1971; 4(1): 1 – 9.Dewar MJ, Dougherty RC. Capítulo 2. Teoría de las perturbaciones de los orbitales moleculares (pmo). En: Química Orgánica. Barcelona: España; Ed. Reverté S.A. 1980. p. 67 – 83.Eliel EL. Conformational analysis in heterocyclic systems: Recent results and applications. Angew. Chem. Int. Ed. Engl. 1972; 11(9): 739 – 50.Hutchins RO, Kopp LD, Eliel EL. Repulsion of syn-Axial electron pairs: The Rabbit-Ear Effect. J. Am. Chem. Soc. 1968; 90(25): 7174 – 5.Lemieux RU, Pavia AA, Martin JC, Watanabe KA. Solvation effects on conformational equilibria: Studies related to the conformational properties of 2-methoxytetrahydropyran and related methyl glycopyranosides Can. J. Chem. 1969; 47(23): 4427 – 39.Edward JT. Stability of glycosides to acid hydrolysis: A conformational analysis. Chem. Ind. 1955; (36): 1102 – 4.Salzner U. Origin of the anomeric effect revisited. Theoretical conformation analysis of 2-hydroxypiperidine and 2-hydroxyhexahydropyrimidine. J. Org. Chem. 1995; 60(4): 986 – 95.Takahashi O, Yamasaki K, Kohno Y, Ohtaki R, Ueda K, Suezawa H, Umezawad Y, Nishio M. The anomeric effect revisited. A possible role of the CH/n hydrogen bond. Carbohydr. Res. 2007; (342): 1202 – 9.Wolfe S. The Gauche effect. Some stereochemical consequences of adjacent electron pairs and polar bonds. Acc. Chem. Res. 1972; 5(3): 102 – 11.Dale J. Exploratory calculations of medium and large rings. Part 1. Conformational minima of cycloalkanes. Act Chem. Scand. 1973; 1(27): 1115 – 29.Singh A, Ganguly B. Probing the influence of solvent effects on the conformational behavior of 1,3-diazacyclohexane systems. J. Phys. Chem. A. 2007; 111(39): 9884 – 9.Schreiber SL. Target-oriented and diversity-oriented organic synthesis in drug discovery. Science. 2000; 287(5460): 1964 – 9.Spandl RJ, Díaz‐Gavilán M, O’Connell KmG, Thomas GL, Spring DR. Diversity-oriented synthesis. Chem. Rec. 2008; 8(3): 129 – 142.Butlerow A. Ueber ein neues Methylenderivat. Liebigs. Ann. Chem. 1860; 115(3): 322 – 7.Jordan TH, Mak tcW. Molecular and crystal structure of hexamethylenetetramine triphenol. J. Chem. Phys. 1970; 52(7): 3790 – 4.Duff JC. A new general method for the preparation of o-hydroxyaldehydes from phenols and hexamethylenetetramine. J. Chem. Soc. 1941; 547 – 50.Duff JC. A new method for the preparation of p-dialkylaminobenzaldehydes. J. Chem. Soc. 1945; 276 – 7.Sommelet M. Sur un mode de décomposition des halogénoalcoylates d’hexaméthylène-tétramine. CR Chim. 1913; (157): 852 – 3.Delépine M. Hexamethylenetetramine compounds. CR Chim. 1895; (120): 743 – 5.Delépine M. Preparation of primary amines. CR Chim. 1897; (124): 292 – 5.Blaevi N, Kolbah D, Belin B, Šunji V, Kajfe F. Hexamethylene tetramine, A versatil reagent in organic synthesis. Synthesis. 1979; 1979(3): 161 – 76.Kaur N, Kishore D. An insight into hexamethylenetetramine: a versatile reagent in organic synthesis. J. Iran. Chem. Soc. 2013; 10(6): 1193 – 228.Galasso V. On the structure and spectroscopic properties of free and protonated adamanzanes. Chem. Phys. 2001; 270(1): 79 – 91.Rivera A, González-Salas D, Ríos-Motta J, Hernández-Barragán A, Joseph-Nathan P. Preferred hydrogen bonding site of 1,3,6,8-tetraazatricyclo[4.3.1.13,8]undecane (tatu) to hydroquinone. J. Mol. Struct. 2007; 837(1-3): 142 – 6.Rivera A, Moyano D, Maldonado M, Ríos-Motta J, Reyes-Velasco A. FT-IR and dFt studies of the proton affinity of small aminal cages. Spectrochim. Acta Part A Mol Biomol Spectrosc. 2009; 74(2): 588 – 90.Rivera A, Núñez ME, Morales-Ríos MS, Joseph-Nathan P. Preparation of cage amine 1,3,6,8-tetraazatricyclo[4.3.1.13,8] undecane. Tetrahedron Lett. 2004; 45(41): 7563 – 5.Rivera A, Núñez ME, Avella E, Ríos-Motta J. An Nmr study of sequential intermediates and collateral products in the conversion of 1,3,6,8-tetraazatricyclo[4.4.1.13,8]dodecane (tatd) to 1,3,6,8-tetraazatricyclo[4.3.1.13,8]undecane (tatu). Tetrahedron Lett. 2008; 49(13): 2154 – 8.Bernal JS. Estudio de la reactividad química de 1,3,6,8-tetrazatriciclo [4.3.1.13,8]undecano (tatu), frente a electrófilos del tipo haluro de alquilo y nucleófilos duros y blandos [tesis doctoral]. Facultad de Ciencias, Universidad Nacional de Colombia; 2012.Hernández MC. Reacción solvent-free de 1,3,6,8-tetrazatriciclo [4.3.1.13,8] undecano (tatu) con fenoles [tesis de maestría]. Facultad de Ciencias, Universidad Nacional de Colombia; 2007.Rivera A, Rojas JJ, Osorio HJ, Ríos-Motta J, Bolte M. Crystal structure of the 1:2 co-crystal of 1,3,6,8-tetraazatricyclo[4.3.1.13,8]undecane (tatu) and 4-chlorophenol. Acta Crystallogr. E Crystallogr. Commun. 2016; 72(11): 1648 – 50.Rivera A, Rojas JJ, Sadat-Bernal J, Ríos-Motta J, Bolte M. Mechanochemical synthesis and crystal structure of a 1:2 co-crystal of 1,3,6,8-tetraazatricyclo-[4.3.1.13,8]undecane (tatu) and 4-chloro-3,5- dimethylphenol. Acta Crystallogr. E Crystallogr. Commun. 2016; 72(11): 1651 – 3.Rivera A, Osorio HJ, Uribe JM, Ríos-Motta J, Bolte M. Crystal structure of the 1,3,6,8-tetraazatricyclo[4.3.1.13,8]undecane (tatu)-4-nitrophenol (1/2) adduct: the role of anomeric effect in the formation of second hydrogen bond interaction. Acta Crystallogr. E Crystallogr. Commun. 2015; 71(11): 1356 – 60.Bischoff CA. Studien über Verkettungen: XXXV. Formaldehyd und zweisäurige Basen. Ber. Dtsch. Chem. Ges. 1898; 31(3): 3248 – 58.Rivera A, Ríos-Motta J. An unusual product obtained from condensation between ethylenediamine and formaldehyde in basic medium. Tetrahedron Lett. 2005; 46(30): 5001 - 4.Murray-Rust P. Crystal and molecular structure of 1,3,6,8-tetraaza tricyclo[4.4.1.13,8]-dodecane, the 2 to 1 condensation product of formaldehyde and 1,2-diaminoethane, and the conformation of this system. J. Chem. Soc. Perkin 2. 1974; 10(0): 1136 – 41.Rivera A, Ríos-Motta J, Bolte M. Redetermination of 1,3,6,8-tetraazatricyclo[4.4.1.13,8]dodecane. Acta Crystallogr. E Struct. Rep. on line 2014; 70(3): o266.Rivera A, Gallo GI, Gayón ME, Joseph-Nathan P. A Novel Mannich type reaction using aminals in alkaline medium. Synth. Commun. 1993; 23(20): 2921 – 9.Rivera A, Quevedo R. Solvent-free Mannich-type reaction of tetraazatricyclododecane (tatd) with phenols. Tetrahedron Lett. 2013; 54(11): 1416 – 20.Rivera A, Nerio LS, Quevedo R. Synthesis of macrocyclic and linear benzylimidazolidine oligomers from solvent free aromatic Mannich-type reaction. Tetrahedron Lett. 2015; 56(44): 6059 – 62.Rivera A, Ríos-Motta J, Quevedo R, Joseph-Nathan, P Nuevos aspectos de la reacción tipo Mannich en medio básico de 1,3,6,8-tetrazatriciclo[4.4.1.13,8] dodecano (tatd) con fenoles. Rev. Colomb. Quím. 2005; 34(2): 117 – 25.Baldwin JE. Rules for Ring Closure. J. Chem. Soc., Chem. Comm. 1976; (18): 734 – 6.Rivera A, Torres OL, Leitón JD, Morales-Ríos MS, Joseph-Nathan P. An efficient approach to 1,3,5-tris-arylhexahydro-1,3,5-triazines. Synth. Commun. 2002; 32(9): 1407 – 14.Smith, M. B., March, J. March’s Advanced Organic Chemistry: Reactions, Mechanisms, and Structure. 6th Ed. Hoboken, New Jersey: usa, John Wiley & Sons, Inc., 2007. p. 798, 1054.Pearson RG. Hard and Soft Acids and Bases. J. Am. Chem. Soc. 1963; 85(22): 3533 – 39.Rivera A, Maldonado M, Núñez ME, Joseph-Nathan P. Nucleophilic substitution at the aminalic carbon of some macrocyclic polyaminals. Heterocycl. Commun. 2004; 10(1): 77 – 80.Katritzky AR, Yang Z, Lam JN. Aminoalkylbenzotriazoles: Reagents for the Aminoalkylation of Electron Rich Heterocycles. Tetrahedron. 1992; 48(23): 4971 – 78.Katritzky AR, Lang H, Lan X. A New Route to N-Substituted Heterocycles. Tetrahedron 1993; 49(14): 2829 – 38.Rivera A, Quiroga D, Jiménez-Cruz L, Fejfarová K, Dušek, M. New cyclic aminals derived from rac-trans-1,2-diaminocyclohexane: synthesis and crystal structure of racemic 1,8,10,12-tetraazatetracyclo[8.3.1.18,12.02,7]pentadecane and a route to its enantiomerically pure (R,R) and (S,S) isomers. Tetrahedron Lett. 2012; 53(3): 345 – 8.Osorio HJ. Estudio de la reactividad química de los aminales asimétricos (2R7R) y (2S,7S)-1,3,10,12-tetrazatetraciclo [8.3.1.18,12.02,7]pentadecano frente a nucleófilos [tesis doctoral]. Facultad de Ciencias, Universidad Nacional de Colombia; 2015.Rivera A, Guevara-Pulido J, Sadat-Bernal J, Ríos-Motta J, Zaragoza G. Structure of the solid state 2:1 molecular of 1,5:3,7-dimethano-1,3,5,7- benzotetrazonine with hydroquinine. Acta Crystallogr. C. 2009; (65): o435 –7.Kuznetsov A, Shukkur A, Kamara K. The synthesis of 1,5:3,7-dimethano 1,3,5,7-benzotetrazecine. Russ. Chem. Bull. 2007; 56(3): 563 – 5.Murray-Rust P, Riddell FG. The stability and conformation of the 1,3,6,8-tetraazatricyclo[4.4.1.13,8]dodecane system: the structure of the condensation product of 1,2-diaminocyclohexane and formaldehyde. Can. J. Chem. 1975; 53(13): 1933 – 5.Quiroga DE. Estudios de la reacción de los aminales quirales (2R,7R,11S,16S)- y (2S,7R,11S,16R)-1,8,10,17-tetrazapentaciclo [8.8.1.18,170.2,70.11,16]eicosano con nucleófilos y electrófilos [tesis doctoral]. Facultad de Ciencias, Universidad Nacional de Colombia; 2013.Rivera A, Pacheco DJ, Ríos-Motta J. Pojarová M, Dušek M. 1,1’-[(2,3,3a,4,5,6,7,7a-Octahydro-1H-1,3-benzimidazole-1,3-diyl)bis (methylene)]-bis(1H-benzotriazole). Acta Crystallogr. E Struct Rep on line. 2011; 67(11): o3071.Murray-Rust P, Smith I. 1,4-Dimethanodibenzo[d,i]-1,3,6,8-tetrazecine Acta Crystallogr. B. 1975; 1975(31): 587 – 9.Volpp G. Zur Struktur einiger Kondensationsprodukte von Formaldehyd mit 1.2-Diaminen. Chem. Ber. 1962; 95(6): 1493 – 4.Rivera A, Maldonado M. Unexpected behavior of 6H,13H-5:12,7:14- dimethanedibenzo[d,i][1,3,6,8]tetraazecine (dmdbta) toward phenols. Tetrahedron Lett. 2006; 47(42): 7467 – 71.Duarte YA. Estudio de la reactividad química del bis aminal N,N ́-bis(1H- benzotriazol-1-il-metil)-1,2-diaminobenceno frente a fenoles. [tesis de maestría]. Facultad de Ciencias, Universidad Nacional de Colombia; 2009.Menschutkin N. Beiträgen zur Kenntnis der Affinitätskoeffizienten der Alkylhaloide und der organischen Amine. Z. Phys. Chem. 1890; 1890(5): 589 – 600.Menschutkin N. Über die Affinitätskoeffizienten der Alkylhaloide und der Amine. Z. Phys. Chem. 1890; 1890(6): 41 – 57.Böhme H, Haake M. Über monoquartäre Salze aus Hexamethylenetetramin und α-halogenierten Aminen. Arch. Pharm. 1967; 300(8): 682 – 3.Bachmann WE, Deno NC. The nitrosation of hexamethylene-tetramine and related compound. J. Am. Chem. Soc. 1951; 73(6): 2777 – 9.Singer R, Vaughan K, Hooper DL. Open chain nitrogen compounds. Part XI. 3,7-bis(arylazo)-1,3,5,7-tetraazabicyclo[3,3,1]nonanes: The reaction of diazonium ions with ammonia-formaldehyde mixtures. Can. J. Chem. 1986; 64(8): 1567 – 72.Vaughan K. Recent progress in the synthesis of bis-triazenes. Org. Preparat. Procedures Int. 2001; 33(1): 59 – 74.Rivera A, Sadat-Bernal J, Ríos-Motta J, Dušek M, Palatinus L. Synthesis and structural studies of a new class of quaternary ammonium salts, which are derivatives of cage adamanzane type aminal 1, 3, 6, 8-tetraazatricyclo[4.3.1.13,8]undecane (tatu). Chem. Cent. J. 2011; 5(55): 1 – 8.Rivera A, González-Salas D. Synthesis and characterization of novel triazenes from the reaction of the cyclic aminal 1,3,6,8-tetraazatricyclo[4.3.1.13,8] undecane (tatu) with diazonium ions. Tetrahedron Lett. 2010; 51(18): 2500 – 4.Rivera A, Gallo GI, Joseph-Nathan P. Nitrosation of aminals: Preparation and characterization of 1,3-dinitrosoimidazolidine. Synth. Commun. 1997; 27(1): 163 – 8.Peori MB, Vaughan K. Synthesis and characterization of novel bis-triazenes: 3,8-di[2-aryl-1-azenyl]-1,3,6,8-tetraazabicyclo[4.4.1] undecanes and 1,3-di- 2-[(4-methoxyphenyl)-1-diazenyl] imidazolidine. The reaction of diazonium ions with ethylenediamine/formaldehyde mixtures. J. Org. Chem. 1998; 63(21): 7437 – 44.Maldonado M. Estudios químico del benzoaminal macrocíclico 6H,13H- 5,12:7,14-dimetanodibenzo[d.i][1,3,6,8]tetrazecina (dbta) [tesis doctoral]. Facultad de Ciencias, Universidad Nacional de Colombia; 2006.Rivera A, Maldonado M, Ríos-Motta J. A Facile and Efficient Procedure for the Synthesis of New Benzimidazole-2-thione Derivates. Molecules. 2012; 17(7): 8578 – 86.540 - Química y ciencias afines::547 - Química orgánicaSíntesis (Química orgánica)Reacciones bioquímicasBiosíntesisQuímica comprehensiva de aminales macrocíclicosLibroinfo:eu-repo/semantics/bookinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_2f33http://purl.org/coar/version/c_970fb48d4fbd8a85TextInvestigadoresPúblico generalORIGINALQuimica_comprehensiva_Aminales.pdfQuimica_comprehensiva_Aminales.pdfLibro Química comprehensiva de aminales macrocíclicosapplication/pdf2453993https://repositorio.unal.edu.co/bitstream/unal/81290/1/Quimica_comprehensiva_Aminales.pdf396cb42c3a8869aa1f899cc9be0c4824MD51LICENSElicense.txtlicense.txttext/plain; charset=utf-84074https://repositorio.unal.edu.co/bitstream/unal/81290/2/license.txt8153f7789df02f0a4c9e079953658ab2MD52THUMBNAILQuimica_comprehensiva_Aminales.pdf.jpgQuimica_comprehensiva_Aminales.pdf.jpgGenerated 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EVESURBIFBPUiBMQSBTRUNSRVRBUsONQSBHRU5FUkFMLiAqTEEgVEVTSVMgQSBQVUJMSUNBUiBERUJFIFNFUiBMQSBWRVJTScOTTiBGSU5BTCBBUFJPQkFEQS4gCgpBbCBoYWNlciBjbGljIGVuIGVsIHNpZ3VpZW50ZSBib3TDs24sIHVzdGVkIGluZGljYSBxdWUgZXN0w6EgZGUgYWN1ZXJkbyBjb24gZXN0b3MgdMOpcm1pbm9zLiBTaSB0aWVuZSBhbGd1bmEgZHVkYSBzb2JyZSBsYSBsaWNlbmNpYSwgcG9yIGZhdm9yLCBjb250YWN0ZSBjb24gZWwgYWRtaW5pc3RyYWRvciBkZWwgc2lzdGVtYS4KClVOSVZFUlNJREFEIE5BQ0lPTkFMIERFIENPTE9NQklBIC0gw5psdGltYSBtb2RpZmljYWNpw7NuIDE5LzEwLzIwMjEK