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1
Robbins, Steven Joseph, and University of Lethbridge Faculty of Arts and Science. "Cyclophanes from kinetically stabilized bis(isobenzofuran)s." Thesis, Lethbridge, Alta. : University of Lethbridge, Deptartment of Chemistry and Biochemistry, 2009, 2009. http://hdl.handle.net/10133/781.
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Isobenzofurans (IBF)s are interesting molecules with regards to their structure and reactivity. The properties of these compounds are investigated through the use of gas phase calculations and kinetic studies. This work provides insight into the aromatic character of IBF and how substituents affect IBF’s reactivity.
Substituted derivatives of naphtho[1,2-c:5,6-c]difuran are synthesized and reacted with tethered bis(dienophile)s to form cyclophanes. Phenyl-substituted naphtho[1,2-c5,6-c]difuran forms only a single isomer when reacted with a tethered bis(acrylate) and a tert-butyldimethylsilyl-substituted derivative exhibits higher selectivity towards cyclophane formation rather than polymer formation. Evidence for strong intramolecular interactions within these cyclophanes is presented as well.
A five-step synthesis of anthra[1,2-c:7,8-c]difuran is developed, although with a poor overall yield. Similar reaction conditions could be applied to the synthesis of anthra[1,2-c:5,6-c]difuran. We also propose the synthesis of two different aromatic belts from these compounds.<br>xxii, 122 leaves : ill. ; 29 cm.
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Fischer, Kristapher Edward, and University of Lethbridge Faculty of Arts and Science. "Synthesis and characterization of novel cyclophanes from 5,5'-bi(isobenzofuran)." Thesis, Lethbridge, Alta. : University of Lethbridge, Faculty of Arts and Science, 2005, 2005. http://hdl.handle.net/10133/255.
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Isobenzofuran has since its discovery proven an important intermediate in the synthesis of novel organic compounds, due to its high reactivity in Diels-Alder reactions. This thesis details the synthesis, purification and characterization of cyclophane compounds derived from a novel analogue of isobenzofuran, 5,5'-bi(isobenzofuran). Because of the relative rarity of molecules containing multiple isobenzofuran units, 5.5'-bi(isobenzofuran) is an excellent candidate for study. Prelminary analysis of an additional novel analogue of isobenzofuran, 5.5'-bis(isobenzofuranyl) acetylene, is also presented.<br>x, 119 leaves : ill. ; 29 cm.
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Thibault, Michelle Elizabeth, and University of Lethbridge Faculty of Arts and Science. "Novel bis(isobenzofuran)s and their utility in the synthesis of cyclophanes." Thesis, Lethbridge, Alta. : University of Lethbridge, Faculty of Arts and Science, 2003, 2003. http://hdl.handle.net/10133/239.
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The synthesis of 1,2-bis(5-isobenzofuranyl)ethene by two routes is described. The first route involved generation of 1,2-bis(5-isobenzofuranyl)ethene from a bis(acetal) precursor under basic conditions. However, the synthesis was lengthy with low-yielding steps, which led to it being abandoned. The second route involved generation of 1,2-bis(5-isobenzofuranyl)ethene from a bis(oxabicyclic) precursor with 3,6-di(2'-pyridyl)-s-tetrazine. Napththo[1,2-c:5,6-c] difuran and 1,2-bis(5isobenzofuranyl)ethene were used to construct novel cyclophanes by double Diels-Alder reactions with bis(maleimide)s. NMR, AM1 modeling, and X-ray studies of the cyclophanes are discused. Attempts to prepare phenanthro[2,3-c:6,7-c] difuran and its cyclophanes are discussed. None was successful, and investigations were hampered by the inability to obtain sufficient quantities of starting materials. Finally, several suggestions are given for improving the syntheses of 1,2-bis(5-
isobenzofuranyl)ethene, phenanthro[2,3-c:6,7-c]difuran, and their cyclophanes. Future directions, such as the functionalization of the double bond of 1,2-bis(5-isobenzofuranyl)ethene, aromatization of the oxabicyclic rings of the cyclophanes, and further X-ray studies are discussed.<br>x, 122 leaves : ill. ; 28 cm.
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Houghton, Tom J. "Synthesis and study of some novel and interesting cyclophanes." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1999. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape7/PQDD_0023/NQ54838.pdf.
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Bartlett, Stephen James. "Synthesis, conformational studies and biological activity of bisindolylmaleimide cyclophanes." Thesis, University of Leeds, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.424060.
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Collins, Shawn K. "Design, synthesis, and applications of novel phenyl/acetylenic cyclophanes." Thesis, University of Ottawa (Canada), 2001. http://hdl.handle.net/10393/9015.
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The synthesis of a novel family of acetylenic cyclophanes via Pd, Cu and Zn catalyzed cross-coupling reactions is described. The cyclophanes were constructed in good yields and X-ray crystal analysis revealed a twisted helical geometry. The nature of the geometry and the ability to complex solvent molecules within the lattice varied upon the number of acetylenic linkages present. Functionalized cyclophanes bearing long alkyl chains based on the helical structures 191 and 213 were also synthesized with potential as novel liquid crystals. Cyclophane 280 showed LC-like behavior when melting was observed under a polarized light microscope. Intramolecular cyclization of paracyclophanes was observed and resulted in cyclophanes, 192 and 203. X-ray crystallographic analysis of the carboxylic acid derivative, 203 revealed the strained nature of the butadiyne bridge. The triple bonds were distorted with bond angles of 163.7° and 163.5°. A novel method for the synthesis of diynes and tetraynes using an in situ desilylation/dimerization procedure was developed but was unsuccessful in producing linear hexaynes. Attempted dimerization of 281 for the synthesis of 282 failed due to a competing intramolecular producing 283. Derivative 307 revealed another highly strained butadiyne bridge possessing bond angles of 164.1° and 153.4°. Metacyclophanes with a termini separation of approximately between 7.8 and 10 A did not undergo intramolecular cyclization. A sequential coupling procedure involving a double dimerization of acetylenes produced traces of the desired cyclophane 282 and no competing intramolecular cyclization products were observed. Progress towards 327, a structural isomer of 282, using an alternative sequential coupling protocol involving a double Sonogashira cyclization is detailed. Attempts to prepare acetylenic cyclophanes bearing metaphenyl/acetylene linkages are described. Initial investigations into the incorporation of thiophenes to acetylenic cyclophanes were thwarted by the instability of the precursor, 372.* *Please refer to dissertation for diagram.
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Heuft, Matthew A. "Design and synthesis of helical acetylenic carbo- and heterocyclic cyclophanes." Thesis, University of Ottawa (Canada), 2004. http://hdl.handle.net/10393/29113.
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The purpose of this research project was to synthesize new acetylenic cyclophanes. These cyclophanes have unusual and aesthetically pleasing structures, pose synthetic challenges, have peculiar reactivity, and often exhibit interesting spectroscopic and physical properties. In addition to the successful synthesis of a number of new cyclophanes, several new synthetic strategies and methods were developed.
A one-pot preparation of arylbutadiynes 95 from chloroenyne 83 and arylhalides was accomplished. This method was used to prepare a variety of arylbutadiynes in 80--95% yields. A procedure was also developed for the in situ desilylation/dimerization of bulky silylalkynes.
A molecular modeling study provided insight into the observed dimerization reaction products of alpha,o-dialkyne precursors. Termini separation distances (r) less than 7 A gave intermolecular coupling, while distances greater than 10 A gave intermolecular reactions. Mixtures of intra- and intermolecular reaction products were obtained when 7 < r > 10 A.
The synthesis of two new C60 acetylenic cyclophanes revealed that the substitution pattern of the capping group controlled the conformation of the molecule. Cyclophane 113 with para-substituted capping groups adopted a helical (chiral) conformation and the isomeric meta-capped cyclophane 123 had a different molecular folding pattern with the potential to be planar.
Two classes of unsaturated cyclophanes were synthesized as ligands for the preparation of chiral, non-racemic helical complexes: A tetramethoxybenzene-capped, C60 acetylenic cyclophane as a potential eta12-bis(arene) ligand, and phenanthrolinophanes as tetradentate pi-coordination ligands. Cyclophane 170 was successfully prepared, but metal complexes of 170 could not be prepared. Phenanthrolinophanes 200, 217, and 227 and their corresponding copper complexes were synthesized by a new, metal-templated procedure. Copper coordination was found to raise the helical isomerization barrier height by over 7 kcal/mol; however, isomerization still occurred at room temperature so enantiopure phenanthrolinophanes could not be isolated.
The first pentacenes with functional groups on the A and E rings have also been synthesized. A highlight of the rapid, four-step synthesis of pentacenes 274 and 275 was the absence of any chromatographic purification. The commercial potential of these new pentacene compounds as organic semiconductors is being investigated in collaboration with the National Research Council of Canada.*
*Please refer to dissertation for diagrams.
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Suvannachut, Kessara. "Scope and mechanism of the rearrangement of alkoxybenzyl anions to alkylphenoxide ions; cyclophanes from 2,6-dimethylanisole." Diss., The University of Arizona, 1989. http://hdl.handle.net/10150/184679.
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Alkoxy alkyl groups migrate to benzylic carbon when alkyl alkylphenyl ethers are treated with n-butyllithium and potassium t-butoxide. For alkyl 2,6-dialkylphenyl ethers, yields of the rearrangement products range from 45-70%. Rearrangement products are obtained in 10-30% yield from other dimethylanisoles and methylanisoles. The reactions appear to proceed by homolytic cleavage of the alkoxy alkyl group of alkoxybenzyl anions followed by recombination of the resulting radical pair in a different way. The reaction is useful for preparing 2,6-dialkylphenols and their corresponding ethers. The rearrangement can be avoided by using methyl ethers and working at or below room temperature. This was shown by reacting the dianion from methyl 2,6-dimathylanisole with dialkyl sulfates to give methyl 2,6-dialkylanisoles, with a,ω-dihalides to give methoxy[n]metacyclophanes (n = 8-15), dimethoxy[n.n]metacyclophanes (n = 5-10) and trimethoxy[S.S.S]metacyclophane, and with oxidizing agents to yield dimethoxy[2.2]metacyclophane.
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Choi, So-Young Amy. "Synthesis, properties, and asymmetric catalysis of chiral cyclophanes and their metal complexes." Connect to a 24 p. preview or request complete full text in PDF format. Access restricted to UC campuses, 2006. http://wwwlib.umi.com/cr/ucsd/fullcit?p3206584.
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Thesis (Ph. D.)--University of California, San Diego, 2006.<br>Title from first page of PDF file (viewed May 10, 2006). Available via ProQuest Digital Dissertations. Vita. Includes bibliographical references (p. 244-263).
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Haque, Rosenani S. M. Anwarul. "Silver, mercury and ruthenium complexes of N-heterocyclic carbene linked cyclophanes." University of Western Australia. Chemistry Discipline Group, 2008. http://theses.library.uwa.edu.au/adt-WU2008.0236.
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This thesis describes the synthesis and isolation of silver, mercury, ruthenium and palladium complexes of bidentate N-heterocyclic carbenes (NHCs), derived from imidazolium-linked cyclophanes and related bis-imidazolium salts. The cyclophane structures contain two imidazolyl links between ortho- and meta- substituted aromatic rings and the related structures are ortho-, meta- and para-xylyl linked bis-imidazolium salts. The complexes have been characterised by NMR spectroscopy and X-ray crystallography. The synthesis of five new silver complexes has been achieved via a simple complexation reaction of the cyclophane and bis-imidazolium salts with the basic metal source Ag2O. The new silver carbene systems are thermally stable. Three of the complexes are dinuclear, cationic complexes, while two are mononuclear complexes, one cationic and one neutral. A number of mono- and di-nuclear mercury(II)-NHC complexes have been synthesised from the ortho- and meta-linked cyclophanes and the related meta-linked bis-imidazolium salts. The mercury complexes were prepared by direct mercuration method using mercury(II) acetate. The syntheses were perfomed in air and the complexes are stable to air and moisture. Mercury complexes I and II represent the first example of mononuclear metal complexes derived from meta-substituted imidazolium-linked cyclophanes. NHC-ligand transfer reactions from NHC-silver complexes and NHC-mercury complexes are described. An ortho-cyclophane ligand was successfully transfered from a silver complex to its palladium counterpart. Furthermore, palladium complex III, bearing a para-xylyl linked bis-NHC ligand, was made by transmetallation from both a silver and mercury complex. This is the first reported NHC-palladium complex of a para-xylyl linked bis-NHC ligand. A new redox transmetallation method for NHC ligand transfer, using a mercury complex, is presented. A palladium complex was made via redox transmetallation using a mercury complex of an ortho-NHC-cyclophane. A ruthenium(II)-NHC complex, IV containing an ortho-cyclophane ligand has been prepared via silver transmetallation and in situ complexation methods. In the transmetallation route, a silver complex of an ortho-cyclophane was treated with RuCl2(PPh3)3 to form IV. This complex represents the first example of a ruthenium complex bearing an NHC-cyclophane ligand, v and is also the first example of a metal complex derived from an imidazolium-linked cyclophane where the arene unit of the cyclophane is also involved in bonding to the metal centre.
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Mannion, Michael R. "Synthesis and chemistry of highly distorted polycyclic aromatic hydrocarbons." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1999. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape7/PQDD_0017/NQ52693.pdf.
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Dikmans, Antonius Josephus. "Synthesis of belt-shaped macrocyclic cyclophanes, Part I, synthesis of key intermediates in the proposed synthesis of (7)- and (8)cyclacenes, Part II, synthesis of key intermediates in a proposed synthesis of a cyclic decaphenylene." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1998. http://www.collectionscanada.ca/obj/s4/f2/dsk2/ftp02/NQ31119.pdf.
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Chernova, Ekaterina. "Synthesis of new [1111]metacyclophane ligands for the formation of molecular coordination networks." Thesis, Strasbourg, 2018. http://www.theses.fr/2018STRAF043/document.
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En termes de chimie supramoléculaire et de tectonique moléculaire, les métacyclophanes [1111] sont des composés attractifs pour la préparation et l’étude de réseaux moléculaires, car la particularité de ces composés est la stabilité exceptionnelle de la conformation l'encombrement stérique entre les groupes ortométhyliques des cycles aryles. Un tel type rigide d'échafaudage moléculaire aussi bien avec la présence de sites de liaison de terminaux est considéré comme un bloc de construction moléculaire très approprié pour la formation de différents types de réseaux moléculaires en utilisant principalement la coordination et la H-bonding. Dans le cadre de ce travail, nous avons étudié le rôle de la nature de la coordination des sites greffés sur le squelette métacyclophane macrocyclique afin d'améliorer leur capacité à former des réseaux de coordination dans la phase cristalline et les systèmes supramoléculaires en solution, une série de nouvelles [1111] métacyclophanes ont été synthétisés et caractérisés en solution et à l'état solide. Leur propension à lier différents cations métalliques dans la phase cristalline ainsi que des complexes en solution ont été étudiés<br>In terms of supramolecular chemistry and molecular tectonics,[1111]metacyclophanes are attractive compounds for the preparation and study of molecular networks since the particular feature of these compounds is determined by exceptional stability of the 1,3-Alternate conformation of their molecular platform due to the steric hindrance between the orto-methyl groups of aryl rings. Such rigid type of molecular scaffold both with presence of terminal binding sites is considered as a very suitable molecular building block for formation of different type molecular networks using primarily coordination and H-bonding. Through this work we investigated the role of the nature of the coordinating sites grafted on the metacyclophane macrocyclic backbone in order to enhance their ability to form coordination networks in the crystalline phase and the supramolecular systems in solution, a series of new [1111]metacyclophanes have been synthesized and characterized in solution and in the solid state. Their propensity to bind different metal cations in the crystalline phase as well as complexes in solution have been studied
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Berns, Caroline. "Synthese und biologische Prüfung funktionalisierter Cyclophane verschiedener Ringgrössen als Oxaanaloga zytotoxischer Naturstoffe." [S.l.] : [s.n.], 2004. http://edoc.ub.uni-muenchen.de/archive/00002177.
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WHITE, JAMES JEFFREY. "ALKYLATION AND OXIDATIONS OF SYMMETRICAL DIMETHYLENEBIPHENYL AND RELATED DIANIONS (CYCLOPHANE, BIPHENYLOPHANE, NMR, CONFORMATION)." Diss., The University of Arizona, 1986. http://hdl.handle.net/10150/183991.
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Bis-benzyl dianions were prepared from the three symmetrical dimethylbiphenyls in yields of 79-86%, and shown to react with a variety of electrophiles on the benzylic carbons. Electrophiles included dimethyl and diethyl sulfate, isopropyl bromide, t-butyl iodide, allyl chloride, trimethylsilyl chloride, trimethylgermyl bromide, and trimethyltin chloride. Reaction of the dianions with (alpha),(omega)-dihalides provides an excellent route to n.0 - and n.0.n.0 cyclophanes. An X-ray study on 14.0 paracyclophane showed it to have a conformation different from that observed in solution by NMR; MM2 calculations were used in determining what the solution conformation is likely to be. Oxidation of the dianions produced the monomer dihydrophenanthrene from the ortho isomer, dimer 2.0.2.0 metacyclophane from the meta isomer, and polymer from the para isomer. An X-ray study on 2.0.2.0 metacyclophane showed it to have the same conformation in the crystal as is observed in solution by NMR. An NMR method for determining the angle of twist in a biphenyl based on the chemical shift of the ortho hydrogens was developed. Many oxidizing agents were evaluated for the oxidation of the dianion from 2,3-dimethyl-1,3-butadiene to 1,2,5,6-tetramethylenecyclooctane; cupric bromide was found to be the best.
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Godbert, Nicolas. "Anthracenediylidene derivatives : control of molecular and supramolecular architecture." Thesis, Durham University, 2002. http://etheses.dur.ac.uk/3818/.
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In the context of new π-donor molecules, extended tetrathiafulvalenes have been widely studies for their use as components of electronically conductive charge-transfer materials. In contrast with the planar π -systems, we have focused our attention on extended tetrathiafulvalenes containing a conjugated anthracenyl spacer (anthracenediylidene derivatives). These TTF derivatives adopt a saddle-shaped conformation in the neutral state and a drastic change of conformation occurs upon oxidation to the dication species. Our main objective was to investigate the molecular and supramolecular architecture of these compounds. At the molecular scale, we synthesised cyclophanes by bridging the preformed anthracene tetrathiafulvalene system and studied their redox properties and crystal packing. We developed the chemistry of anthracenediylidene derivatives in order to direct the supramolecular architecture by secondary interactions (hydrogen-bonding, π-π stacking). Finally, we also investigated the incorporation of anthracenediylidene units inside dendritic structures in order to study the highly charged species formed upon oxidation.
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Le, Bras Nathalie. "Nouveaux cyclophanes et cryptands : synthese, etude des conformations, electro-reduction." Rennes 1, 1992. http://www.theses.fr/1992REN10137.
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L'addition de l'acrylate de methyle sur un dialdehyde, en presence de diazabicyclooctane, suivie d'une reaction d'acetylation est une voie d'acces simple a des precurseurs de cyclophanes et de cryptands. L'utilisation de divers dialdehydes comme l'isophtalaldehyde, des isophtalaldehydes substitues, le furanne 2,5-dicarboxaldehyde et un dialdehyde qui derive de la disubstitution d'un dihalogenure d'alkyle par un hydroxybenzaldehyde a permis de generaliser cette methode de synthese. Des cryptands symetriques, des orthocyclophanes et un metacyclophane sont ainsi obtenus par action de l'ammoniaque. L'addition de diacetates, autre que le para di(acetoxy-1 methoxycarbonyl-2-propene-2 yl) benzene, sur le diaza 7,7 paracyclophane tetraene donne des cryptands dissymetriques et un macrobicycle asymetrique. D'autres nucleophiles, tels que le sulfure de sodium et des amines primaires, ont ete utilises. Les modifications de conformation sous l'effet de la protonation, de la complexation d'acides ou des substitutions, ont ete examinees. Le diaza 7,7 paracyclophane tetraene et le cryptand correspondant ont fait l'objet d'une etude electrochimique. La reaction est etudiee par voltammetrie cyclique
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DANSOU, AHOEFA BENEDICTE. "Recherches sur la synthese totale des 7. 0 metacyclophanes appartenant a la serie de la myricanone." Le Mans, 1999. http://www.theses.fr/1999LEMA1002.
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Nous avons envisage differentes voies d'acces aux metacyclophanes biarylheptanoides du groupe de la myricanone, l'idee de base etant de realiser la liaison biarylique a un stade precoce de la synthese et de proceder par la suite a la fermeture du cycle par condensation de thorpe-ziegler. La construction de la liaison biarylique a fait l'objet de 2 approches synthetiques differentes : (i) la premiere met en jeu, dans une reaction de couplage dissymetrique d'ullmann, deux halogenures d'aryle portant chacun une chaine laterale fonctionnalisee ; (ii) la deuxieme oppose a un acide areneboronique dans la reaction de couplage dissymetrique de suzuki, un halogenure d'aryle porteur ou non d'une chaine laterale fonctionnalisee. Les resultats obtenus mettent en evidence l'efficacite de la methode de suzuki lors du couplage d'un halogenure d'aryle (porteur ou non de chaine laterale fonctionnalisee) avec un acide areneboronique dont le noyau aromatique est enrichi par des groupements electrodonneurs. Deux nouveaux biaryles substitues, precurseurs potentiels des metacyclophanes du groupe de la myricanone, ont ete soumis aux conditions de condensation de thorpe-ziegler, en vue d'acceder aux metacyclophanes escomptes. Ce travail decrit les premiers exemples de tentatives de cyclisation intramoleculaire de thorpe-ziegler, (i) d'un biaryle substitue comportant sur chacun des deux cycles aromatiques une chaine fonctionnalisee a 4 atomes de carbone, reliee a une position meta de chacun des deux cycles aromatiques, et (ii) d'un biaryle substitue comportant sur l'un des deux cycles une chaine fonctionnalisee a 5 atomes de carbone et sur l'autre une chaine fonctionnalisee a 3 atomes de carbone ; ces 2 chaines etant reliees a une position meta de chacun des deux cycles aromatiques.
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Hesler, Valerie Jane. "N-Heterocyclic carbene-metal complexes derived from imidazolium-linked cyclophane and biimidazolium salts." University of Western Australia. School of Biomedical, Biomolecular and Chemical Sciences, 2008. http://theses.library.uwa.edu.au/adt-WU2009.0088.
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This thesis presents an investigation into the synthesis of metal complexes of (Nheterocyclic carbene)-based cyclophanes. There were three main areas of focus: synthesis and complexation of bis(4,5-dihydroimidazolium) salts; the synthesis and complexation of phenol-functionalised imidazolium cyclophanes; and the synthesis and complexation of (N-heterocyclic carbene)-based cyclophanes by C-C bond activation of biimidazolium salts with electron-rich metals. The synthesis of xylyl-linked bis(4,5-dihydroimidazolium) salts was investigated. Attempts to prepare these compounds by the cyclisation of a tetraamine (linear or macrocyclic) were unsuccessful due difficulties in preparing the tetraamines. The target compounds could be prepared by adapting the methods developed for the synthesis of bis(imidazolium) salts however problems associated with purification and stability of the products prevented complexation studies. A series of phenol-, phenoxide- and anisole-functionalised imidazolium cyclophanes were prepared. Their structural properties were investigated using dynamic nmr studies and X-ray crystallography. Complexation of the functionalised cyclophanes was investigated. The phenol cyclophane I formed a dinuclear complex with mercury(II). This complex is the first example of a complex derived from a phenol-functionalised imidazolium cyclophane. However the anisole cyclophane II and the unsymmetrical phenol/ortho cyclophane III were unable to form complexes possibly due to steric hindrance and instability of the cyclophane respectively. Preliminary complexation studies of the bis(imidazolium)phenol V suggested that complexation with palladium(II) and mercury(II) were possible but more work is required to determine the optimum reaction conditions. A series of biimidazolium salts VI (both new and known) were prepared. Previously reported biimidazolium salts have very low solubility in common solvents therefore the incorporation of long alkyl chains to the bridging group was investigated as a means to improve the solubility. The structure of the salts was explored using a range of techniques including dynamic nmr spectroscopy, cyclic voltammetry, UV/Visible spectroscopy, X-ray crystallography and mass spectrometry. Some of the biimidazolium salts were able to rotate about the C2-C2' bond and the free energy of activation for this process was estimated using dynamic nmr studies. C-C bond activation of the biimidazolium salts with palladium(0) was used to form a series of palladium(II) complexes (VII) of (NHC)-based cyclophanes. These reactions are the first examples of the synthesis of bis(NHC) complexes by C-C bond activation. The reactivity of the biimidazolium salts with palladium(0) was compared to their solution structure and it was found that only the biimidazolium that were able to rotate about the C2-C2' bond could react with palladium(0).
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Berns, Caroline. "Synthese und biologische Prüfung funktionalisierter Cyclophane verschiedener Ringgrößen als Oxaanaloga zytotoxischer Naturstoffe." Diss., lmu, 2004. http://nbn-resolving.de/urn:nbn:de:bvb:19-21774.
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Thapa, Mahendra. "Design, synthesis, and anti-influenza activity of substituted quercetins and progress towards the synthesis of mini graphenes like hexa-peri-benzocoronene cyclophane." Diss., Kansas State University, 2012. http://hdl.handle.net/2097/15077.
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Doctor of Philosophy<br>Department of Chemistry<br>Duy H. Hua<br>The first chapter of the thesis involves the design, synthesis, and anti-influenza activity of quercetin derivatives. Influenza viruses are important pathogens that cause respiratory infections in humans and animals. In addition to vaccination, antiviral drugs against influenza virus play a significant role in controlling viral infections by reducing disease progression and virus transmission. Plant derived polyphenols are associated with antioxidant activity, anti-carcinogenic, and cardio- and neuro-protective actions. Some polyphenols, such as resveratrol and epigallocatechin gallate (EGCG), showed significant anti-influenza activity in vitro. The antiviral effects of isoquercetin were greater than that of quercetin with lower IC[subscript]5[subscript]0 values and higher in vitro therapeutic index. Various phenolic esters, alkoxy and aminoalkoxy derivatives of quercetin were synthesized by functionalization of C3, C3’, and C5 hydroxyl groups. Antiviral activities of these synthesized compounds were tested against influenza virus (porcine H1N1 strain). Quercetin-3-gallate which is structurally similar to EGCG showed greater antiviral activity among the synthesized compounds. Its antiviral activity was comparable to that of EGCG with better in vitro therapeutic index.
Second chapter in the thesis involves the progress towards the synthesis of mini graphenes like hexa-peri-benzocoronene cyclophane (HBCC). Bilayered graphenes are highly conducting materials with potential application in electronic devices and in lithium ion batteries. Despite great potential, bilayer graphenes with defined distance between the two layers have not been achieved through chemical synthesis. Chemical synthesis of hexa-peri-benzocorenene cyclophane (HBCC) from commercially available p-xylene was carried out. Final product, presumably compound 90 (the structure has not been completely characterized), is insoluble in
all tested solvents including aqueous acids and organic solvents such as DMSO, DMF, benzene, 1,2-dichlorobenzene, dichloromethane, THF, hexanes and diethyl ether. The insoluble nature of the final product restricted the analysis to UV-visible spectroscopy. Synthesis of soluble analog incorporating the long chain ether groups is being investigated in Dr. Hua’s laboratory.
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Hickman, Hazel Alice. "Towards the synthesis of alkoxy-substituted [2.2]para-cyclophenes and [2.2]para-cyclophane-1-enes : tailored monomers for the preparation of well-defined, functionalised PPV." Thesis, University of Leicester, 2005. http://hdl.handle.net/2381/30100.
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This thesis describes a route towards the synthesis of alkoxy-functionalised [2.2] para-cyclophenes and [2.2]-para-cyclophane-1-enes as possible monomers for the preparation of functionalised PPVs via ROMP, using their corresponding alkoxy-functionalised stilbenes as precursors to furnish the desired cyclophenes through a ring-closing reaction. Chapter 1 is divided into three sections, A, B and C. Section A introduces the concept of conducting and electroluminescent polymers, with particular emphasis upon polyacetylene and PPV. Section B discusses stilbenes in detail, while section C examines the structure, preparation and reactivity of cyclophanes and cyclophenes, specifically [2.2] para-cyclophane and [2.2] para-cyclophene. Chapter 2 explains the synthesis of a series of alkoxy-substituted benzaldehydes, designed as easily accessible, readily functionalised precursors to alkoxy-substituted stilbenes, while Chapter 3 shows how these alkoxy-substituted benzaldehydes can be transformed into stilbenes, through the application of either the McMurry, Wittig, or Horner-Wittig reactions. Chapter 4 describes further transformations of alkoxy-substituted stilbenes, with emphasis placed upon achieving ring-closing to furnish the desired [2.2] para-cyclophenes and [2.2] para-cyclophene-1-enes. Preparation of an oligomeric form of PPV from the same stilbene precursors is also discussed, and the photophysics of both this oligomer and its related stilbenes is investigated. Chapter 5 outlines an alternative route towards alkoxy-functionalised [2.2] para-cyclophenes, via a Ramberg-Backlund rearrangement of functionalised cyclic dithioethers, and Chapter 6 gives overall conclusions for this thesis, briefly introducing possible further studies to be undertaken on this topic. Chapter 7 contains experimental details and characterisation data for all compounds prepared during the course of this work.
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Haeg, Marietta Eileen. "Synthesis and study of two tribridged cyclophanes." 1988. http://catalog.hathitrust.org/api/volumes/oclc/19356895.html.
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Thesis (Ph. D.)--University of Wisconsin--Madison, 1988.<br>Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 265-268).
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"Synthesis and conformational behavior of dibenzo[2.2]metaparacyclophanediene." Chinese University of Hong Kong, 1988. http://library.cuhk.edu.hk/record=b5885976.
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Wang, Huan. "The intramolecular benzannulation reaction and its application in the synthesis of cyclophanes /." 2000. http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&res_dat=xri:pqdiss&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&rft_dat=xri:pqdiss:9965172.
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"Part I, Synthesis and characterization of fluorene-based statistical copolymers: Part II, Regiospecific synthesis of substituted [2.2]paracyclophanes." 2004. http://library.cuhk.edu.hk/record=b5892117.
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Kam-Hung Low.<br>Thesis submitted in: December 2003.<br>Thesis (M.Phil.)--Chinese University of Hong Kong, 2004.<br>Includes bibliographical references.<br>Abstracts in English and Chinese.<br>Table of contents --- p.i.<br>Acknowledgements --- p.vi.<br>Abbreviations --- p.vii.<br>Abstract --- p.viii.<br>Abstract (Chinese) --- p.x.<br>Chapter Part I --- Synthesis and Characterization of Fluorene-Based Statistical Copolymers<br>Chapter Chapter I --- Introduction --- p.1<br>Chapter 1. --- Background --- p.1<br>Chapter 2. --- rinciple of Electroluminescence --- p.2<br>Chapter 3. --- Electroluminescence from conjugatedolymers --- p.4<br>Chapter 4. --- Device configurations --- p.6<br>Chapter 4.1 --- Electrodes selection --- p.8<br>Chapter 4.2 --- Charge injection and transporting layers --- p.9<br>Chapter 5. --- Device characterizations --- p.12<br>Chapter 6. --- Blue-light emittingolymers --- p.14<br>Chapter 6.1 --- Fluorene homopolymers --- p.16<br>Chapter 6.2 --- Fluorene copolymers --- p.19<br>Chapter 6.3 --- Aggregation studies ofolyfluorenes --- p.22<br>Chapter 7. --- Synthetic measures toward conjugatedolymers --- p.28<br>Chapter Chapter II --- Results and discussion --- p.30<br>Chapter 1. --- Synthesis --- p.30<br>Chapter 1.1 --- olyfluorene synthesis --- p.30<br>Chapter 1.2 --- Fluorene-based statistical copolymers --- p.34<br>Chapter 1.2.1 --- Fluorene-biphenyl copolymers --- p.34<br>Chapter 1.2.2 --- Fluorene-［2.2]paracyclophane copolymers --- p.37<br>Chapter 2. --- Structural characterizations --- p.40<br>Chapter 2.1 --- NMR spectroscopic data analyses --- p.40<br>Chapter 2.2 --- Gelermeation chromatographic analyses --- p.44<br>Chapter 2.3 --- Thermal analyses --- p.47<br>Chapter 3. --- Opticalroperties characterizations --- p.50<br>Chapter 3.1 --- UV-visible absorptions --- p.50<br>Chapter 3.2 --- hotoluminescences --- p.53<br>Chapter 3.2.1 --- hotoluminescences in solutions --- p.53<br>Chapter 3.2.2 --- hotoluminescences in solid thin films --- p.59<br>Chapter 4. --- Device fabrications --- p.61<br>Chapter 5. --- I-V characterizations --- p.64<br>Chapter 6. --- Electroluminescences --- p.66<br>Chapter Chapter III --- Conclusion --- p.68<br>Chapter Chapter IV --- Experimental --- p.70<br>Reference --- p.77<br>Appendix NMR spectra --- p.82<br>Chapter Part II --- Regio-Specific Synthesis of Functionalized [2.2]PARACYCLOPHANES<br>Chapter Chapter I --- Introduction --- p.102<br>Chapter 1. --- Background --- p.102<br>Chapter 2. --- Synthetic Route to [2.2]Paracyclophane --- p.103<br>Chapter 2.1 --- Macrocyclization via Wurtz coupling --- p.103<br>Chapter 2.2 --- Extrusion of small gaseous molecules form macrocyclicrecursors --- p.106<br>Chapter 2.3 --- Dimerization of/p-xylylene --- p.108<br>Chapter 2.4 --- Miscellaneous methods --- p.110<br>Chapter 3. --- Synthetic Routes to Substituted [2.2]Paracyclophanes --- p.111<br>Chapter 3.1. --- Functionalization of [2.2]pracyclophane --- p.114<br>Chapter 3.1.1 --- reparation of mono-substituted [2.2]paracyclophanes --- p.114<br>Chapter 3.1.2 --- reparation of di-substituted [2.2]paracyclophanes --- p.117<br>Chapter 3.1.3 --- reparation of tri-substituted [2.2]paracyclophanes --- p.120<br>Chapter 3.1.4 --- reparation of tetra-substituted [2.2]paracyclophanes --- p.120<br>Chapter 3.1.5 --- Functional group conversions in [2.2]paracyclophanes --- p.121<br>Chapter Chapter II --- Syntheticlans --- p.124<br>Chapter Chapter III --- Results and Discussion --- p.129<br>Chapter 1. --- Effect ofolymerization inhibitor --- p.130<br>Chapter 2. --- "Synthesis of 4,12-disbstituted [2.2]paracyclophanes" --- p.132<br>Chapter 2.1 --- "Synthesis of 4,12-dibromo[2.2]paracyclophane" --- p.132<br>Chapter 2.2 --- "Synthesis of 4,12-dichloro[2.2]paracyclophane" --- p.134<br>Chapter 2.3 --- "Synthesis of 4,12-dimethyl[2.2]paracyclophane" --- p.135<br>Chapter 3. --- "Synthesis of 4,7,13,16-tetrasubstituted [2.2]paracyclophanes" --- p.137<br>Chapter 3.1 --- "Synthesis of 4,7,13,16-tetrabromo[2.2]paracyclophane" --- p.137<br>Chapter 3.2 --- "Synthesis of 4,7,13,16-tetrabromo[2.2]paracyclophane" --- p.138<br>Chapter 4. --- "Synthesis of 4,8,12,16-tetrasubstituted [2.2]paracyclophane" --- p.139<br>Chapter 4.1 --- "Synthesis of 4,8,12,16-tetrabromo[2.2]paracyclophane" --- p.139<br>Chapter 5. --- Summary --- p.141<br>Chapter Chapter IV --- Conclusion --- p.145<br>Chapter Chapter V --- Experimental --- p.146<br>References --- p.160<br>Appendix I X-ray crystallographic data --- p.162<br>Appendix II NMR spectra --- p.183
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"Synthesis of [beta]-ketomacrolides via 1-oxa[n]meta-cyclophanes and a new route to (+-)-patulolide C." Chinese University of Hong Kong, 1994. http://library.cuhk.edu.hk/record=b5895379.
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by Fong Sun.<br>On t.p., "+" appears over "-".<br>Thesis (M.Phil.)--Chinese University of Hong Kong, 1994.<br>Includes bibliographical references (leaves 41-43).<br>Acknowledgements --- p.i<br>Contents --- p.ii<br>Abstract --- p.iii<br>Abbreviations --- p.iv<br>Chapter I --- Introduction<br>Chapter I-1 --- General background --- p.1<br>Chapter I-2 --- Literature survey --- p.3<br>Chapter I-2-1 --- Ley's approach to β-ketomacrolides --- p.3<br>Chapter I-2-2 --- Weiler's approach to β-ketomacrolides --- p.4<br>Chapter I-2-3 --- Macrocyclic β-ketomacrolides formation through sulfide contraction ´ؤIreland's approach --- p.5<br>Chapter II --- Result and Discussion<br>Chapter II-1 --- General strategy for the synthesis of 1 -oxa[n]metacyclophanes --- p.7<br>Chapter II-2 --- l-Oxa[n]metacyclophanes as masked β-ketomacrolides synthons --- p.9<br>Chapter II-3 --- Application to the synthesis of natural products --- p.10<br>Chapter II-4 --- An alternate approach for the synthesis of (2E)-2-dodecen-l 1-olide´ؤA structural proof --- p.15<br>Chapter III --- Conclusion --- p.17<br>Chapter IV --- Experimental --- p.18<br>Chapter V --- References --- p.41<br>Chapter VI --- Spectra --- p.44
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"Synthesis of Dibenzo [2.2] paracyclophane and its related compounds." Chinese University of Hong Kong, 1987. http://library.cuhk.edu.hk/record=b5885801.
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"Part I, Synthesis and conformational behavior of metaparacyclophane: Part II, Total syntheses of optically active neolignans containing a dihydrobenzo[b]furan skeleton." 1997. http://library.cuhk.edu.hk/record=b6073016.
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by Mabel Siu-Man Yuen.<br>Thesis (Ph.D.)--Chinese University of Hong Kong, 1997.<br>Includes bibliographical references (p. 146-161).<br>Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web.<br>Mode of access: World Wide Web.
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Hwa, Ching-Lun, and 花敬倫. "Synthesis of Bicyclo[2.2.2]octene-Based Molecular Crabs and Cyclophanes." Thesis, 2005. http://ndltd.ncl.edu.tw/handle/10666684383952896473.
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博士<br>國立中正大學<br>化學所<br>94<br>The synthetic route to the U-shaped, multi-functionalized diol 70 begins from the Diels-Alder adduct 67. Through five steps lead to diol 70. The U-shaped diol 70 reacted with benzyl bromide, 4-bromobenzyl bromide, 4-iodobenzyl bromide, 9-(bromomethyl)anthracene, 1-(bromomethyl)pyrene, isomeric bromomethylpridines via Williamson ether synthesis to construct a series of molecular crabs. It also reacted with acetic anhydride, benzoyl chloride, benzoic acid, 9-fluorenone- 2-carboxylic acid via base-promoted esterification to afforded another series molecular tweezers with crab-shaped structure. The self-assembled intramolecular p-stacking of chromophore in 105, 106, 117 and 118 with the distance about 3.4 Å, and the consequent p-p interactions were revealed by the X-ray crystal structure or its luminescence property. On the other hand, the bis-meta-pyridyl crab 110 complexation with silver(I) afforded a (1+1) metallo-bridged cyclophane 113. And the silver(I)-complex 114 from bis-ortho-pyridyl crab 111 is a (2+2) dimeric dimetallocyclophane. The U-shaped diol 70 reacted with a,a’-dibromo-p-xylene and a,a’-dibromo- m-xylene via Williamson ether synthesis afforded (1+1) cyclophanes, (2+2) cyclophanes and oligomers. In these cases, (2+2) cyclophanes were major products. Diol 70 reacted with a,a’-dibromo-o-xylene afforded both (2+2) cyclophane and oligomers. There has none (1+1) cyclophane being isolated.
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Zhang, Limin. "The synthesis and chemistry of the cyclophanenes and their metal complexes." Thesis, 1992. https://dspace.library.uvic.ca//handle/1828/9592.
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A new synthetic route to cyclophanenes 56, starting from an appropriate 2,6-dihalogen-substituted toluene via monothiacyclophanes as intermediate compounds, was developed. By this method, anti-5,8,13-16-tetramethyl [2,2] (1,3)cyclophan-1-ene, 56b, and anti-4,6,8,12,14,16-hexa-methyl [2,2] (1,3)cyclophan-1-ene, 56c, were first synthesized as well as three new monothiacyclophanes, anti-9,17-dimethyl-2-thia [3,2] (1,3) cyclophane, 72a, anti-6,9,14,17-tetramethyl-2-thia [3,2] (1,3) cyclophane, 72b, anti-5,7,9,13,15,17-hexamethyl-2-thia [3,2] (1,3) cyclophane, 72c. An X-ray structural determination of the monothiacyclophane 72a revealed an anti-stepped geometry of the molecule and that the aromatic rings were bent outward in a slightly distorted boat form. A reciprocal relationship between deviations of the inner carbons from their basal planes and distances between the inner carbons was found by comparison of X-ray data of four metacyclophanes.
Several tricarbonylchromium(0) and η5-cyclopentadienyl-iron(I) complexes of cyclophanenes 56 were also prepared for the first time. The complexation effect and ring current reduction effects in these complexes were investigated through studies of their proton nmr spectra. An X-ray structure analysis of anti-8,16-dimethyl [2,2] (1,3) cyclophan-1-ene-cyclopentadienyliron(I), 105a, was determined and it was found that the bridge double bond (1.345A) has a cis geometry but with very large torsional angles: 24.7° for C-C=C-C and 41.6° for H-C=C-H.
The bridge chemistry of cyclophanenes 56 and their metal complexes was investigated through some selected reactions. It was found that the cyclophanenes 56 were easily oxidized in attempted electrophilic additions to the bridge double bond. Bromination of the cyclophanene-iron complexes 105b and 105c did give the desired bromine adducts. However, it was found that the reactivity of the bridge double bond in cyclophanenes 56 is very low since most of the attempted reactions failed to give the desired products.
The first synthesis of the (η6, η6-anti-4,6,8-trimethyl [2,2] (1,3) cyclophan-1,9-diene)-bis(tricarbonylchromium(0)), 133, was achieved through the dithiacyclophane route. An X-ray structure analysis of 133 was also determined and found that the two aromatic rings were inclined at 19.8° with respect to each other.<br>Graduate
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Ellis-Holder, Keisha. "Efforts toward the synthesis of imidazolidinyl and benzimidazolidinyl N-heterocyclic carbenes in cyclophanes." 2005. http://proquest.umi.com/pqdweb?did=982802371&sid=16&Fmt=2&clientId=39334&RQT=309&VName=PQD.
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Thesis (Ph.D.)--State University of New York at Buffalo, 2005.<br>Title from PDF title page (viewed on Mar. 14, 2006) Available through UMI ProQuest Digital Dissertations. Thesis adviser: Diver, Steven T. Includes bibliographical references.
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Iyer, Vivekanantan S. "Approaches to bridged annulenes using both classical and reactive intermediates: the synthesis of the first diatropic bridged thiaannulene and several fused dihydropyrenes." Thesis, 1994. http://hdl.handle.net/1828/5941.
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Li, Jiang. "Cyclophanes, transannular inverse electron demand Diels-Alder reactions and a formal total synthesis of (±)-strychnine /." 2002.
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Chen, Yen-Fei, and 陳彥妃. "(I) Anion-Recognition Studies of Inorganic Re(I)-Based Cyclophanes Containing Dipyridyl-Amide Ligands(II)Synthesis and Photophysical Properties of Halotricarbonylrhenium(I) with Pd(II) or Pt(II) Complexes." Thesis, 2006. http://ndltd.ncl.edu.tw/handle/05389661143643708813.
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碩士<br>國立中正大學<br>化學所<br>94<br>Recently, supramolecular design, synthesis, and applications have been extensively studied. The desired functionality in metal-containing molecular squares may be introduced by employing functional ligands or properly functionalized metal corners with appropriate size and shape. This research is classified into two parts. In the first part, we are successful to utilize flexible ligand N,N’-4-dipyridyl oxalamide (L1) and ligid ligand N,N’-bis(pyridine)benzene-1,3-dicarboxamide (L2) as bridging ligands for the construction of molecular square (1) and molecular loop (2) with Re(I) ion as metal corners, respectively. Besides, we use highly directional hydrogen bonds as a means of controlling self-assembly in supramolecular systems, and upon the anion-recognition studies have also been examined for 1. The binding affinity for F－, CN－, OAc－ and Cl－ have been known, and the stoichiometry in the reaction between 1 and various anions (F－, CN－, OAc－ and Cl－) with TBA salts are confirmed to be 1:1 from a Job Plot. Based on the results from 1H NMR titration spectra and absorption titration spectra, both show the titration undergoing two-step processes. Thus, we suggest that the titration process first proceeds hydrogen-bonding interactions and then proton transfer (deprotonation) reactions.
In the second part, we design and synthesize two new dicarboxylic acid ligands, 2,2’-bipyridine-5,5’-dicarboxylic acid (m-dca-bpy) and 2,2’-bipyridine-4,4’-dicarboxylic acid ( p-dca-bpy) as bridging ligands for the synthesis of luminescent Re(I) complexes, m-Re and p-Re, respectively. In addition, the titration data indicate a 1:2 stoichiometry in two cases resulting from the 1H NMR spectra and absorption spectra. The Pd(II) or Pt(II) ions have been incorporated the m-Re and p-Re units, and the absorption and luminescence studies also carried out.
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"Synthetic studies of benzoannulated metaparacyclophanes." Chinese University of Hong Kong, 1986. http://library.cuhk.edu.hk/record=b5885653.
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"Synthetic study of 1,2:8,9-dibenzo [2,2] metacyclophane." Chinese University of Hong Kong, 1987. http://library.cuhk.edu.hk/record=b5885832.
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Sigritz, Rainer. "Synthese, Struktur und Reaktivität von ansa-Ferrocenen." Doctoral thesis, 2010. https://nbn-resolving.org/urn:nbn:de:bvb:20-opus-50003.
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In der vorliegenden Arbeit wird die Synthese von [2]Ferrocenophanen auf verschiedenen Wegen gezeigt. Neben der vollständigen Charakterisierung der Verbindungen wird auch deren Reaktivität untersucht. So wird gezeigt, dass mit den Elementen der Gruppe 16, sowie mit späten Übergangsmetallkomplexen eine Insertion in die Element-Element Bindung der Brücke statt finden kann. Darüber hinaus wird ausgehend von einem [2]Diboraferrocenophan eine katalytische Syntheseroute zur Diborierung von Alkinen entwickelt, sowohl unter homogenen als auch unter heterogen Bedingungen. Ausgehend von einem [2]Ferrocenophan wird eine neue Syntheseroute zur Darstellung von Ferrocenylboronsäureestern gezeigt<br>Within this thesis, the synthesis of [2]ferrocenophanes is presented in different ways. Besides, the compounds are not only fully characterized, but also their reactivity is examined. It is shown, that on the addition of group 16 elements or late transition metal complexes, an insertion into the element-element bond can take place. Furthermore, starting from a [2]diboraferrocenophane, a synthetic protocol for the homogeneous and the heterogeneous catalyzed diboration of alkynes was developed. Starting from a [2]ferrocenophane, a new pathway for the synthesis of ferrocenyl boronic acids is presented
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Cumaraswamy, Abbarna. "New Synthetic Strategies, Spectral and Molecular Recognition Studies on Verdazyl-Derived [n]-Paracyclophanes." Thesis, 2010. http://hdl.handle.net/1807/30144.
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Verdazyl radicals are a unique class of stable radicals that have found uses as reporter molecules in biological systems, substrates for molecular-based magnets and mediators in living radical polymerizations. Over the past few years, our laboratory has pioneered the use of verdazyl radicals as substrates in 1,3-dipolar cycloaddition reactions to provide unique small molecule five-membered ring systems containing structural features commonly found in therapeutic agents. As an extension to this work we became interested in seeing whether this chemistry could be applied to the synthesis of macrocyclic scaffolds, in particular cyclophanes. Cyclophanes have been attractive synthetic targets for organic chemists because of their unique structural properties, conformational behaviours and molecular recognition capabilities. Presented in this thesis is the successful demonstration of the extension of the verdazyl chemistry to novel [n]-paracyclophanes. The structural features and conformational biases of these molecules as evidenced by 1H-NMR and X-ray crystallography are highlighted along with molecular recognition studies.
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Mager, Julian. "Synthese, Struktur und Reaktivität neuer [n]Metallocenophane." Doctoral thesis, 2013. https://nbn-resolving.org/urn:nbn:de:bvb:20-opus-78384.
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Das Ziel dieser Arbeit bestand in der Synthese und Charakterisierung neuer Metallocenophane mit Sila-, Bora- und Stannabrücken. Sowohl für die Synthese über 1,1'-dimetallierte Metallocene als auch für die Synthese über die sogenannte flytrap-Methode sind dihalogenierte Brücken erforderlich. Für die Synthese neuer Trisilametallocenophane wurde deshalb eine verbesserte Synthese für 1,3-Diphenyl- und 1,3-Dichlorotrisilane erarbeitet. Die für die flytrap-Methode benötigten Liganden konnten aus 1,3-Dichloro-2,2-diisopropyltrisilan durch die Umsetzung mit den lithiierten Ringsystemen Lithiumindenid, Lithiumfluorenid und Lithiumoctafluorenid erhalten werden. Die dadurch dargestellten, zweifach arylsubstituierten Trisilane konnten anschließend erfolgreich mit BuLi zweifach lithiiert werden Das für die Darstellung von Triborametallocenophanen benötigte 1,3-Dibromo-1,2,3-tris(dimethylamino)triboran(5) sowie dessen Vorstufe 1,1,2,3,3-Pentakis-(dimethylamino)triboran(5) wurde über die bekannte Syntheseroute von Nöth et al. dargestellt. Durch eine Verbesserung der Reaktionsbedingungen konnten die Ausbeuten von 23% auf 36% bzw. auf 71% erhöht werden. Außerdem wurde eine Einkristallröntgenstrukturanalyse erhalten. Metallocenophane der 8. Gruppe werden meist durch Reaktion der 1,1'-dilithiierten Metallocenene mit dihalogenierten Brücken dargestellt. Um die Synthese von Rutheno- und Osmocenophanen zu ermöglichen, wurden Ruthenocen und Osmocen mit BuLi und pmdta als Hilfsbase lithiiert und erstmals als Feststoffe isoliert. Diese wurden mittels NMR-Spektroskopie und Einkristallröntgenstrukturanalyse untersucht, wodurch gezeigt wurde, dass sie wie 1,1'-Dilithioferrocen und 1,1'-Dilithometalloarenophane im Feststoff als dimere Verbindungen vorliegen. Aus thf konnte zusätzlich die Einkristallröntgenstrukturanalyse des thf-stabilisierten 1,1'-Dilithioruthenocen-Dimers erhalten werden Mit den in dieser Arbeit synthetisierten 1,3-Dichlorotrisilanen und 1,1'-Dilithioferrocen wurden die entsprechenden Trisilaferrocenophane synthetisiert und mittels NMR-Spektroskopie untersucht. Von der iPropyl-substituierten Verbindung konnte zusätzlich die erste Einkristallröntgenstrukturanalyse eines Trisilaferrocenophans erhalten werden Durch eine Umsetzung von 1,1‘-Dilithioruthenocen und –osmocen mit dem Diisopropyltrisilan konnten die ersten Trisilametallocenophane von Ruthenium und Osmium dargestellt werden. Durch die Umsetzung von 1,1‘-Dilithioosmocen mit Tetramethyldichlorodisilan gelang die Darstellung des ersten Osmocenophans mit einer zweiatomigen Brücke. Von Tetramethyldisilaosmocenophan konnte eine Einkristallröntgenstrukturanalyse erhalten werden. Die Syntheseroute von Tetra-tert-butyldistannaferrocenophan von Braunschweig et al. konnte erfolgreich auf die Synthese der Ruthenium- und Osmiumanaloga übertragen werden. Die zinnverbrückten Metallocenophane konnten NMR-spektroskopisch und durch eine Einkristallröntgenstrukturanalyse charakterisiert werden. Die von Wrackmeyer et al. und Braunschweig et al. bekannte Insertion von Chalkogenen in die Zinn-Zinn-Bindung konnte ebenfalls für die Verbindungen gezeigt werden. Dabei konnte eine deutliche Verkürzung der Reaktionszeit von 10 d auf 1 d durch die Zugabe von einem Äquivalent pmdta zur Reaktionsmischung erreicht werden. Mit der Ligandenvorstufe 1,2-Bis(lithio-cyclopentadienid)-1,1,2,2-tetra-tert-butyldistannan konnten über die flytrap-Methode die Distannametallocenophane von Cobalt und Nickel synthetisiert werden. Zudem konnten beide Verbindungen mit Ferroceniumhexafluorophosphat einfach oxidiert werden. Die beiden 19-Valenzelektronenverbindungen wurden mittels ESR-Spektroskopie untersucht. Von beiden Cobaltocenophanen sowie vom Nickelocenophan konnte eine Einkristallröntgenstrukturanalyse erhalten werden<br>The aim of this work consisted in the synthesis and characterization of new metallocenophanes with sila-, bora-, and stanna-bridges. Dihalogenated bridges are necessary both for the synthesis via 1,1’-dimetalated metallocenes and for the synthesis via the so-called flytrap method. Therefore, the first step consisted in the development of an improved synthetic procedure for the synthesis of 1,3-diphenyl-, and 1,3-dichlorotrisilanes. The ligands necessary for the flytrap method were obtained by reacting 1,3-dichloro-2,2-diisoporpltrisilan with the lithiated ring systems lithium indenide, lithium fluorenide, and lithium octafluorenide. Subsequently, a twofold lithiation of these molecules was carried out successfully with BuLi. 1,3-Dibromo-1,2,3-tris(dimethylamino)triborane(5), which is necessary for the synthesis of triborametallocenophanes, and its precursor 1,1,2,3,3,-pentakis(dimethylamino)-triborane(5) were synthesised via the synthetic procedure of Nöth et al.. By adjusting the reaction parameters, the yields were improved from 23% to36% and to 71%. Additionally, a solid state structure was obtained. Metallocenophanes of group 8 are generally synthesised by reacting 1,1'-dilithiated metallocenes with dihalogenated bridges. To achieve the synthesis of ruthenocenophanes and osmocenophanes, ruthenocene and osmocene were lithiated with BuLi and pmdta and isolated for the first time as solids. These were analysed via NMR spectroscopy and molecular structure analysis. This showed that both are dimers in the solid state, similar to 1,1'-dilithioferrocene and 1,1'-dilithiometalloarenophane. Additionally, the solid state structure of the thf-stabilised 1,1'-dilithioruthenocene dimer was obtained. Using the trisilanes and 1,1’-dilithioferrocene, new trisilaferrocenophanes were synthesised and analysed via NMR spectroscopy. Additionally, the first example of a crystal structure analysis of a trisilaferrocenophane was obtained. By reacting 1,1’-dilithioruthenocene and -osmocene with diisopropyltrisilane, the first trisilametallocenophanes of ruthenium and osmium were obtained. The reaction of 1,1’-dilithioosmocene with Me4Si2Cl2 resulted in the first osmocenophane with a diatomic bridge Also, a crystal structure analysis was obtained. The earlier synthesis of tetra-tert-butyldistannaferrocenophane by Braunschweig et al. was successfully transferred to the synthesis of the ruthenium and osmium analogues. The tin-bridged metallocenophanes were characterised by NMR spectroscopy and molecular structure analysis. The insertion of chalcogens into the tin-tin bond, previously reported by Wrackmeyer et al. and Braunschweig et al. was also shown. By adding one equivalent of pmdta to the reaction mixture, the reaction time was shortened significantly from 10 d to less than1 d. Using the ligand precursor 1,2-bis(lithio-cyclopentadienide)-1,1,2,2-tetra-tert-butyldistannane and the flytrap method, the distannametallocenophanes of cobalt and nickel were synthesised. Additionally, both compounds were oxidised by one electron using ferrocenium hexafluorophosphate. The 19 valence electron compounds were analysed via ESR spectroscopy. Crystal structure analyses were obtained from both cobaltocenophanes as well as the nickelocenophane
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Kearney, Patrick C. "Studies of Organic Molecule Recognition by Synthetic Cyclophane Receptors in Aqueous Media." Thesis, 1994. https://thesis.library.caltech.edu/7662/1/Kearney_pc_1994.pdf.
Full textAbstract:
<p>The behaviors of six new cyclophane receptors for organic guest molecules in
aqueous media are reported. These new hosts are modifications of more basic
parent structures, and the main goal of their examination has been to determine
how the modifications affect host selectivity for cationic guests. In particular, we
have been interested in determining how additional non-covalent binding
interactions can complement the cation-π interactions active in the parent
systems. Three types of modifications were made to these systems. Firstly,
neutral methoxy and bromine substituents were added to produce four of the six
new macrocycles. Secondly, two additional aromatic rings (relative to the parent
host) capable of making cation-π interactions with charged guest species were
appended. Thirdly, a negatively charged carboxyl group was attached to
produce a cavity in which electrostatic interactions should enhance cationic guest
binding. ^1H-NMR and circular dichroic techniques were employed to determine
the binding affinities of a wide variety of organic guests for the parent and
modified structures in aqueous media.</p>
<p>Bromination of the parent host greatly enhances its binding in a general
fashion, primarily as the result of hydrophobic interactions. The addition of
methoxy groups does not enhance binding, apparently as a result of a collapse of
the hosts into a conformation that is not suitable for binding. The appendage of
extra aromatic rings enhances the binding of positively charged guests, most
likely in response to more complete encapsulation of guest species. The addition
of a negatively charged carboxylate enhances the binding to only selective
groups of cationic guests. AM1 calculations of the electrostatic potentials of
several guests molecules suggests that the enhancements seen with the modified
receptor compared to the parent are most likely the result of close contact
between regions of highest potential on the guest and the appended carboxylate.</p>
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Kraft, Mario. "[1]- und [2]Borametallocenophane der Gruppe-4-Metalle : Synthese, Struktur und katalytische Aktivität." Doctoral thesis, 2005. https://nbn-resolving.org/urn:nbn:de:bvb:20-opus-14689.
Full textAbstract:
In der vorliegenden Arbeit wird über die Synthese, Struktur und katalytische Aktivität von borverbrückten Gruppe 4 Metallocenophanen berichtet, die als Katalysatoren in der Ziegler-Natta-artigen Olefinpolymerisation eingesetzt werden können. Neben den bereits bekannten [1]Borametallocenophanen wurden weitere Komplexe mit unterschiedlichen Substituenten, als auch die bislang unbekannten [2]Borametallocenophane synthetisiert und charakterisiert. Vergleichende Polymerisationsstudien einer Reihe von unterschiedlich substituierten [n]Borametallocenophanen (n = 1,2) wurden unter definierten Standardbedingungen durchgeführt, um einen möglichen Einfluss der am Boratom gebundenen Substituenten zu beobachten. Weitergehende Untersuchungen bezogen sich auf den Einfluss dieser Substituenten auf sterische und elektronische Einflüsse, die mit den Polymerisationsergebnissen korreliert wurden. Hierbei wurden die sterischen Einflüsse der verschiedenen Substituenten anhand der Kristallstrukturen festgemacht; elektronische Einflüsse sollten anhand von CO Schwingungen, die mittels Infrarotspektroskopie beobachtet werden können, von korrespondierenden Carbonylkomplexen und alternativ mittels 91Zr-NMR Spektroskopie untersucht werden<br>In this thesis the synthesis, structure and catalytic activity of boron bridged Group 4 metallocenophanes are reported. These type of complexes are suitable catalyst precursors for the Ziegler-Natta-type olefin polymerization. Besides the known [1]borametallocenophanes new complexes with different substituents as well as the so far unknown [2]borametallocenophanes were synthesized and characterized. A series of differently substituted [n]borametallocenophanes (n = 1,2) were used under defined polymerization conditions, to study a possible influence of the substituents at boron on the catalytic performance. Furthermore, the influence of steric and electronic parameters was evaluated. X-ray structural determinations were used to determine steric changes imposed by the different substituents. Electronic changes were analyzed with the aid of infrared spectroscopy by comparison with the corresponding carbonyl complexes and, alternatively, by 91Zr NMR spectroscopy
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Kao, Chia-Chi, and 高家齊. "Synthesis and structure study of copper(I) or silver(I) complexes of 2,11-dithia-4,5,6,7,8,9-hexahydro-[3.3]-cyclophane." Thesis, 2004. http://ndltd.ncl.edu.tw/handle/e7czn7.
Full textAbstract:
碩士<br>靜宜大學<br>應用化學研究所<br>92<br>Cyclophane possess the nature of rigidity and the character of electric current of the benzene rings, which are able to influence each other between two ring. Many researchers are interested in the nature. We mainly discuss to synthesize cyclophanes which contain a cyclophane ring instead of an arene ring and these derivatives of cyclophanes with metals.
Under a high-dilute condition, a series of substituted 3.10-dithiahexahydro[3.3]paracyclophane were prepared by a coupling reaction of cis-1,4-bis(mercaptomethyl)benzene and substituted α,α''-dibromo-p-xylene, in an alkaline ethanol solution. We take advantage of dithiahexahydro[3.3]paracyclophane and metal’s compounds with Cu+ and Ag+ to synthesize forming difference complex compounds of metals which are used difference solvents with the mode of the diffusivity slowly in two layers difference solvents. We confer the changes and difference of these complex compounds of metals by X-Ray Diffractometer.
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Berns, Caroline [Verfasser]. "Synthese und biologische Prüfung funktionalisierter Cyclophane verschiedener Ringgrößen als Oxaanaloga zytotoxischer Naturstoffe / von Caroline Berns." 2004. http://d-nb.info/971997632/34.
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Stork, Timon [Verfasser]. "Synthese und Anwendung neuer, Cyclophan-basierter N-heterocyclischer Carbene sowie Studien zur Darstellung cyclischer bismetallischer Amonoylid-Carbenkomplexe / vorgelegt von Timon Stork." 2010. http://d-nb.info/1010476092/34.
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