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1
Sherman, D. J. "Studies on some platinum metal compounds." Thesis, University of Oxford, 1987. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.382671.
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Lambert, Ronald J. W. "The bonding, synthesis and electrochemistry of some iron-sulphur-nitrosyl compounds." Thesis, University of St Andrews, 1990. http://hdl.handle.net/10023/14972.
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Salts of the bls(μ-thiosulphato-S)-bis(dinitrosylferrate)(2-) anion, [Fe2(S2o3)2(NO)4]2- can be prepared by the reaction of iron(ll)/thiosulphate mixtures with nitrite ion. The crystal structure of {(Ph3P)2N}2[ Fe2(S203)2(NO)4] reveals it to adopt a trans structure. 15N n.m.r. studies of this salt also show it to adopt the trans structure in solution. The anion reacts with thiolate ion, RS-, to provide good yields of Fe2(SR)2(NO)4; e.p.r. studies show the mononitrosyl [Fe(N0)(SR)3]3− to be a major intermediate in this reaction. Salts of the Black Roussin ion, [Fe4S3(NO)7]- react with aryldiazonium salts, ArN2+ , to produce Fe2(SAr)2(NO)4. 13C n.m.r. studies of Fe2(SC6H4F)2(NO)4 reveal it to exist in a 1:1 ratio of cis and trans isomers. Reaction of the Black anion with trialkylsulphonium or sulphoxonium salts leads to the metathesis product. The crystal structure of Me3S[Fe4S3(NO)7] shows no evidence for the closure of the iron-sulphur cage by the sulphur of the Me3S cation. Reaction of the Black anion with trialkyloxonium salts provides good yields of Fe2(SR)2(NO)4. Electrochemical studies on Fe2(SR)2(NO)4 by conventional cyclic voltammetry shows two chemically and electrochemically reversible one electron reductions to produce [Fe2(SR)2(NO)4]− and [Fe2(SR)2(NO)4]2−. The monoanion is a paramagnetic complex with g= 1.995; coupling to four equivalent nitrogens shows the presence of a delocalised electron. The electrochemical behaviour of the dianion is dependent on the electrode material; reversible on a glassy carbon electrode but quasi-reversible on platinum. Fe2(SR)2(NO)4 also exhibits a three electron oxidation; the anodic current of which increases in the presence of primary amines. Electrochemical studies on the Black Roussin ion and its selenium analogue [Fe4Se3(NO)7]− show similar electrochemical responses: three reversible one electron reductions and an irreversible multielectron oxidation. Extended Huckel molecular orbital calculations on [Fe2S2(NO)4]2− , Fe2(SMe)2(NO)4 and [Fe2(S203)2(N0)4]2− reveal little direct Fe-Fe interaction in these complexes. Reduction or oxidation would result in the addition or removal of electron density from orbitals of mainly Fe-S character. An electrochemical study of Fe(NO)(S2C N R2)2 by cyclic voltammetry shows a reversible one electron reduction and an Irreversible oxidation in tetrahydrofuran and dichloromethane. In acetonitrile the reduction of the complex is coupled to a chemical step making the reduction chemically irreversible at low scan rates. The observed variation of E with R is due to the inductive effect of R.
3
Yousif-Ross, Sue A. "Studies toward the synthesis of phosphido-bridged iron carbonyl and nitrosyl compounds /." The Ohio State University, 1988. http://rave.ohiolink.edu/etdc/view?acc_num=osu1487596307356516.
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Leung, Hiu-chi, and 梁曉詞. "Syntheses, reactivities and biological activities of ruthenium azido, nitrido and nitrosyl complexes supported by tetradentate tertiaryamine ligands." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2010. http://hub.hku.hk/bib/B43703732.
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Eroy-Reveles, Aura Alegra. "Synthesis of photoactive manganese nitrosyl compounds and materials for the light controlled release of nitric oxide /." Diss., Digital Dissertations Database. Restricted to UC campuses, 2008. http://uclibs.org/PID/11984.
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Legoupy, Stéphanie. "Synthèse et réactivité de nouveaux complexes organométalliques chiraux du rhénium." Rennes 1, 1997. http://www.theses.fr/1997REN10148.
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Le travail présenté dans ce mémoire concerne la synthèse et la réactivité de complexes du rhénium. De nouveaux complexes organométalliques chiraux du rhénium des alcools propargyliques et homoallylique ont été synthétisés. Des alcools allyliques secondaires et 1,2-disubstitues ont été coordonnés à l'entité chirale (#5C#5H#5)Re(No)(Pph#3)#+Bf#4#-. Dans le cas du 3-buten-2-ol complexe, les deux diastéréoisomères ont pu été séparés. L'étude de la réactivité de ces complexes du rhénium a montré qu'ils sont compatibles avec des réactions d'oxydation, de Wittig, de réduction, d'estérification, de chloration, de bromation et de fluoration. L'entité organométallique (#5C#5H#5)Re(No)(Pph#3)#+Bf#4#- s'est montrée un bon groupement protecteur d'une seule double liaison au cours de ces réactions. Les substitutions allyliques, catalysées par un acide de Lewis, sur les complexes du rhénium des alcools allyiques ont été étudiées. Quelque soit le nucléophile, ces réactions sont régio- et stéréosélectives et se font avec rétention de configuration. Un mécanisme impliquant un complexe -allyl dicationique du rhénium a été proposé. Le rôle activateur du rhénium a été mis en évidence.
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Richter-Addo, George Bannerman. "Synthetic utilization of the redox properties of some group 6 organometallic nitrosyl complexes." Thesis, University of British Columbia, 1988. http://hdl.handle.net/2429/29174.
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The redox behavior of a series of organometallic complexes containing Cp'M(NO) groups (Cp' = ƞ⁵-C₅H₅(Cp) or ƞ⁵-C₅Me₅(Cp*) ; M = Mo or W) has been investigated both by cyclic voltammetry and by chemical means. The neutral 16-electron Cp'Mo(N0)X₂ compounds (X = CL, Br or I) undergo a single, essentially reversible, one-electron reduction in CH₂CL₂/O.1M [n-Bu₄N]PF₆ at relatively low potentials (<-0.1 V vs SCE). The electrochemically observed reductions can be effected on a preparative scale by employing CP₂C0 as the chemical reductant. The isolable 17-electron [Cp'Mo (NO)X₂]•⁻ radical anions are cleanly reconverted to their 16-electron neutral precursors by treatment with [Cp₂Fe]BF₄. In contrast, the Cp'W(NO)I₂ compounds undergo rapid decomposition to their [Cp'W(NO)I]₂ monohalo dimers upon electrochemical reduction.
Electrophiles NE⁺ (E = O or ϱ-O₂NC₆H₄N) undergo unprecedented insertions into the Cr-C ϭ-bonds of CpCr(NO)₂R complexes (R = Me, CH₂SiMe₃ or Ph) to afford [CpCr(N0)₂{N(E)R}]⁺ cationic complexes. Present evidence is consistent with these insertions occurring via charge-controlled, intermolecular attacks by NE⁺ at the Cr-R groups in classical SE2 processes. The newly-formed N(E)R ligands function as Lewis bases through nitrogen atoms toward the formally 16-electron [CpCr(NO)₂]⁺ cations and may be displaced from the chromium's coordination sphere by the more strongly coordinating CL⁻ anion. The resulting CpCr(NO)₂CL can be reconverted to CpCr(NO)₂R. thereby completing a cycle by regenerating the initial organometallic reactant. The entire sequence of stoichiometric reactions forming the cycle thus constitutes a selective method for the formation of new carbon-nitrogen bonds, the net organic conversions mediated by the CpCr(NO)₂ group being NE⁺ + R⁻ → N(E)R.
The electrophilic [Cp'M(NO)₂]⁺ cations (Cp'=Cp or Cp* ; M = Cr, Mo or W) condense with methyl propiolate and 2,3-dimethyl-2-butene to afford cationic organometallic lactone complexes. These complexes undergo facile
⍜-dealkylation to yield the neutral Cp'M(NO)₂(ƞ¹-lactone) derivatives. Furthermore, the neutral Cp'W(NO)₂(ƞ¹-lactone) compounds decompose in air to their Cp'W(O)₂(ƞ¹-lactone) dioxo products.Science, Faculty of
Chemistry, Department of
Graduate
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Rahman, Mohammad Saifur. "SYNTHESIS AND PHOTOCHEMICAL STUDIES OF NEW PHOTOACTIVATABLE NITROXYL (HNO)-RELEASING COMPOUNDS." Kent State University / OhioLINK, 2019. http://rave.ohiolink.edu/etdc/view?acc_num=kent1574853859162083.
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Leung, Hiu-chi. "Syntheses, reactivities and biological activities of ruthenium azido, nitrido and nitrosyl complexes supported by tetradentate tertiary amine ligands." Click to view the E-thesis via HKUTO, 2010. http://sunzi.lib.hku.hk/hkuto/record/B43703732.
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Sharp, William Brett. "Synthesis and ligand reactivity of group 6 organometallic nitrosyl complexes." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 2001. http://www.collectionscanada.ca/obj/s4/f2/dsk3/ftp04/NQ61173.pdf.
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Blanchard, Shannon Storm 1969. "The synthesis and reactivity of low valent technetium nitrosyl complexes." Thesis, Massachusetts Institute of Technology, 1994. http://hdl.handle.net/1721.1/32134.
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Bohnenberger, Jan [Verfasser], and Ingo [Akademischer Betreuer] Krossing. "Synthesis of novel homoleptic and heteroleptic transition metal carbonyl and nitrosyl cations." Freiburg : Universität, 2020. http://d-nb.info/122063140X/34.
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Nesbitt, Elizabeth. "Synthesis of a Novel Organoplatinum (II) Compound." Scholarship @ Claremont, 2015. http://scholarship.claremont.edu/scripps_theses/572.
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Preliminary NMR data indicate that a new platinum compound, assigned (TpyO)PtMe (TpyO = 2,6-bis-(2’pyridyl)-4-pyridonate), can be synthesized by the addition of impure trans-(DMSO)2PtMeCl to impure 2,6-bis(2’-pyridyl)-4-hydroxypyridine (TpyOH) in the presence of NEt3 in about 10% yield. It is likely that the yield could be increased by using purified TpyOH and (DMSO)2PtMeCl. The metalation step of the synthesis was also attempted using (COD)PtMeCl but was unsuccessful with either Na2CO3 or NEt3 as bases, most likely due to the chelate effect of the bidentate COD. Future work with (TpyO)PtMe will include the addition of H+/D+ to generate the platinum (IV) complex, [(TpyO)Pt(Me)(H)]+, and/or the σ-complex [(TpyO)Pt(Me-H)]+ in order to examine the kinetic, isotope, and thermodynamic effects of the resulting reductive elimination reaction.
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Clifton, Mary Jennifer. "Studies in stereoselective synthesis via reissert compound chemistry." Thesis, This resource online, 1991. http://scholar.lib.vt.edu/theses/available/etd-08222009-040256/.
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Boyes, Scott Antony. "Enantioselective synthesis using bromoacetals." Thesis, Sheffield Hallam University, 1998. http://shura.shu.ac.uk/19380/.
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A brief overview of why it is important to prepare a chiral compound as a specific enantiomer rather than as a racemate is discussed along with several general strategies on how they maybe prepared. The area of research into the preparation of racemic and enantiomerically pure arylpropanoic acids is briefly reviewed by reference to some of the more important synthons. Some of the more general procedures that have been developed for the construction of arylpropanoic acids are discussed. The preparation of substituted alkyl aryl ketones and their subsequent two step conversion into diastereomerically enriched dimethyl tartrate (S)-bromoalkyl aryl acetals is described. An investigation into the effects of solvent, source of anhydrous acid, workup procedure, source of bromine and temperature upon the bromination of these dimethyl tartrate acetals is discussed. Direct conversion of these diastereomerically enriched dimethyl tartrate (S)-bromoalkyl aryl acetals into enantiomerically pure (S)-bromoalkyl aryl ketones and their subsequent conversion into (S)-bromoalkyl aryl esters via a Baeyer-Villiger reaction is described. Hydrolysis of these (S)-bromoalkyl aryl esters followed by treatment with diazomethane afforded the corresponding methyl (S)-bromoalkyl esters with minimal racemisation, while treatment of these (S)-bromoalkyl aryl esters with an amine gave the corresponding amide with minimal racemisation. Reduction with sodium borohydride at low temperature of a (S)-bromoalkyl aryl ketone afforded exclusively the corresponding (1S,2S) alkyl aryl bromohydrin as predicted using the Felkin-Anh model. Stereospecific conversion of our diastereomerically enriched dimethyl tartrate (S)-bromoalkyl aryl acetals into (S)-arylcarboxylic acids using a silver promoted or solvent promoted rearrangement is discussed. Subsequent conversion of these (S)-arylcarboxylic acids into the corresponding Boc amide via a modified Curtius rearrangement is described. Possible further uses of dimethyl tartrate bromoacetals leading to the synthesis of highly functionalised lactones, lactols, epoxides, chiral diacids, diamines, chiral ligands, resolving agents etc are also discussed.
16
Olivo, Horacio F. "Studies on the stereo- and regiochemistry of [4+2] cycloaddition of nitroso compounds to chiral halobenzenediols. Total synthesis of lycoricidine." Diss., Virginia Tech, 1992. http://hdl.handle.net/10919/40018.
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Engesser, Tobias Adrian [Verfasser], and Ingo [Akademischer Betreuer] Krossing. "The synthesis of reactive gold(I) and phosphorus cations with nitrosyl salts of weakly coordinating anions." Freiburg : Universität, 2016. http://d-nb.info/111971771X/34.
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Kurth, Franz [Verfasser]. "Efficiency Determination and Synthesis of Complex-Compound Planetary Gear Transmissions / Franz Kurth." München : Verlag Dr. Hut, 2012. http://d-nb.info/1029400172/34.
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Veillard, Nicolas. "Design and synthesis of compound libraries containing the 2(1h)-pyrazinone moiety." Thesis, Institute of Cancer Research (University Of London), 2008. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.509709.
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Aslam, Shazia Nusrat. "Synthesis and biological evaluation of cicerfuran an antifungal compound from chickpea roots." Thesis, University of Greenwich, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.401042.
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Mohamed, Safwat. "Parallel synthesis of small molecule compound libraries : isoform selective Rho-Kinase inhibitors." Thesis, University of British Columbia, 2015. http://hdl.handle.net/2429/54300.
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The objective of this thesis was to use parallel synthesis to build small molecule libraries of novel compounds with potential as isoform selective type II rho-kinase (ROCK1/2) inhibitors. Considerable effort is ongoing to identify isoform selective ROCK inhibitors, as hyperactivity of the ROCK is implicated in cardiovascular diseases, cancer, diabetes and many other diseases that affect millions of Canadians, and billions of people worldwide. In the absence the extensive structural details of the type II kinase inhibitor binding mode, we have used an empirical approach to the design of type II ROCK inhibitors, based on the conception that such molecules correspond to elongated structures with H-bonding functional elements in their central portion, a motif at one end that mimics the adenine ring in ATP, and a hydrophobic moiety at the other end of the molecule that will interact with an allosteric pocket in the ATP binding region of the kinase. Based on these very general structural requirements, eleven different representative libraries of novel compounds (not described in CAS) were designed and synthesized. In the initial series of compounds, a 2-pyridinone motif was employed as the hinge binding element, and the central portion corresponded to carboxamide substituted oxazoline, oxadiazole, or 2-aminothiazole system, joined through the amide bond to a set of structurally diverse aromatic, heteroaromatic and benzylamine subunits, corresponding to the diversity elements. The preliminary assay results demonstrated that, overall, these compounds were weak and non-selective ROCK1/2 inhibitors when compared to H-1152 as a positive control at 10 μM concentration. However, further structural modification revealed the interest in using an indazole motif as the hinge binder in conjunction with the 2-aminothiazole carboxamide linker. Indeed, more potent activities were observed in the single point assay for a significant portion of the libraries of molecules built around these structural components. Further evaluation of 18 active compounds in a 10-point assay, by Invitrogen, to determine IC50’s revealed that indazole-based inhibitors are active at low micromolar concentrations (1-10 µM), but do not display any significant isoform selectivity.Pharmaceutical Sciences, Faculty of
Graduate
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Rice, M. J. "Synthetic models of cytochrome P450 and photosynthesis." Thesis, University of Cambridge, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.233252.
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The work presented in this dissertation describes the prepartion and characterisation of various strapped porphyrin compounds which are designed to model cytochrome P450 and the charge separation in photosynthesis. The major part of this work is concerned with models of cytochrome P450. After a brief introduction to the philosophy of modelling, there follows a review of work on the enzyme and various compounds which are designed to reproduce the enzymic characteristics. The synthesis of two singly bridged porphyrins is reported. These incorporate a pendent methyl ester in the centre of the strap and aim to mimic the proposed acylation step in the catalytic cycle. Evaluation as models was performed by a series of experiments involving the addition of potassium superoxide to the manganese complexes of these compounds. Characterisation of the mode of reactivity required the use of many physical techniques and necessitated the synthesis of a radio-labelled sample of one of the porphyrins. The results obtained suggest that superoxide binds preferentially to the bridge-free face of the macrocycle. Doubly bridged analogues of the above models were prepared which force the two faces of the porphyrin to be equivalent. Superoxide binding studies indicated a different mode of reactivity to the singly bridged models, for one of the compounds, and experiments to distinguish between possible interpretations of the results are suggested. A crown ether thiolate doubly bridged porphyrin was prepared as a model for the carbon monoxide complex of the enzyme. This was characterised by ultraviolet spectroscopy and attempts to produce a stable crystalline adduct are described. The remaining part of this work concerns a model for the charge separation process in photosynthesis. A discussion of natural systems and previous models is followed by a description of a tetraene pyromellitimide doubly bridged porphyrin, which shows significant quenching of the porphyrin fluorescence.
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Fernandez, Salazar Franz Rene. "A thermodynamic study on cation dibenzocryptand 222 and cation-dibenzo 18 crown 6 complexation in non-aqueous media." Thesis, University of Surrey, 1988. http://epubs.surrey.ac.uk/844484/.
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A general review on macrocyclic ligands with particular emphasis to dibenzocryptand 222 and dibenzo 18 crown 6 is given in the first part of the thesis (Chapter 1). This is followed by an exhaustive literature survey on the stability constants (hence free energies of complexing), enthalpies and entropies of metal cations with cryptands (dibenzocryptand 222, benzocryptand 222, cryptand 222) and crown ethers (dibenzo 18 crown 6, benzo 18 crown 6, 18 crown 6) in water and in non-aqueous solvents at 298.15 (Chapter 2). The experimental part (Chapter 3) also includes a detailed description of the principals involved in calorimetry as well as the methods used for the calculation of reaction enthalpies. Stability constant data for alkali-metal and silver cations with dibenzocryptand 222 in five dipolar aprotic solvents (N,N dimethyl-formamide, dimethylsulphoxide, acetonitrile, propylene carbonate and nitromethane) at 298.15 K are reported. These data are used to calculate the standard free energies of the complexation process involving metal(I) cations and dibenzocryptand 222 in the dipolar aprotic solvents. Free energy data are combined with enthalpy data obtained in this work in order to evaluate the entropies of complexation of these cations with dibenzocryptand 222 in these solvents. A linear correlation previously shown for metal(I) cations and cryptand 222 in DMF, Me2SO, AN, PC and NM between entropies of complexing and entropies of solvation of metal(I) cations in dipolar aprotic solvents is also found for dibenzocryptand 222. The results obtained in this thesis provide further evidence that the complexation process with metal (I) cations and cryptands is mainly controlled by the state of solvation of the cation in the solvent. Enthalpies of solution of dibenzocryptand 222 in the dipolar aprotic solvents are reported and the thermodynamic parameters for the extraction process in the water + nitromethane solvent system as described by M+(H2O) + 22B2B(NM) → M+22B2B (NM) are calculated (Chapter 4). Thermodynamic parameters of solution and transfer of dibenzo 18 crown 6 are discussed with respect to corresponding data for dibenzocryptand 222. The transfer free energies of metal ion dibenzocoronates from water to a number of solvents are calculated and it is shown that, unlike cryptates, there is an interaction between the complexed cation and the solvent in metal ion dibenzocoronates in dipolar aprotic media. Thermodynamic parameters of complexation for alkali-metal and dibenzo 18 crown 6 in acetonitrile are reported. The complexation process seems to be enthalpically and entropically controlled (Chapter 5). Synthesis of crown compounds and heats of solution of 18 crown 6 carried out at several temperatures as well as DeltaCp values in water are presented in Chapter 6.
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Waterfield, P. C. "Novel C-organostannyl heterocycles." Thesis, University of Bath, 1988. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.384138.
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Fretwell, Mark. "Asymmetric synthesis of cyclic ethers via a tandem carbenoid insertion and ylide rearrangement strategy." Thesis, University of Nottingham, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.324477.
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Yanto, Yanto. "Evaluation of novel enoate reductases as potential biocatalyst for enantiomerically pure compound synthesis." Diss., Georgia Institute of Technology, 2011. http://hdl.handle.net/1853/39576.
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Asymmetric synthesis with biocatalyst has become an increasingly interesting and cost effective manufacturing process in fine chemicals, pharmaceuticals, and agrochemical intermediates. Enoate reductases from the Old Yellow Enzyme family offer high substrate efficiency, region, stereo-, and enantioselectivity in the catalyzed biotransformations. Asymmetric reduction of activated C=C bond is one of the most widely applied synthetic tools for the potential to generate up to two stereogenic centers in one step reaction. The thesis contributed to the development and characterization of the Old Yellow Enzyme family members including NRSal from Salmonella typhimurium, YersER from Yersinia bercoviei, KYE1 from Kluyveromyces lactis, and XenA from Pseudomonas putida. We explored the possible new chemistry, gathered further understanding of enzymes functionality and biochemistry, evaluated parameters such as enzyme stability, productivity, and selectivity, and improved enzyme specificity through computational guided protein engineering method. In overall, the increasing knowledge about this Old Yellow Enzyme family together with recent advances in biotechnology renders the enoate reductases a tool of choice for industrial applications.
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Edge, Mark. "Studies of potential intermediates for the total synthesis of the antitumor compound (+)-pancratistatin." Thesis, Georgia Institute of Technology, 1992. http://hdl.handle.net/1853/27358.
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Tsay, Fuh-Rong. "Synthesis and 2-D NMR Analysis of a New Phenyl-Substituted Polycyclic Compound." Thesis, University of North Texas, 1991. https://digital.library.unt.edu/ark:/67531/metadc504049/.
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Diels-Alder [4+2] cycloaddition of a mixture of 1- and 2 methylcyclopentadiene to 2-phenyl-g.-benzoquinone affords a mixture of four nd cycloadducts. A single, isomerically pure cycloadduct was isolated by careful column chromatography. Stereospecific reduction of this material with sodium borohydride and cerium(III) chloride 'affords a single, isomerically pure tricyclic diol. The structures of the cycloadduct and this tricyclic diol, established via analysis of their one- and two-dimensionial NMR spectra, were shown to be (1-methyl-5-phenyltricyclo[6.2.1.02,7]undec a-4,9 diene-3,6-dione and 1-methyl-5-phenyltricyclo[6.2.1.0 2 ,7 ]undeca-4,9-diene t.&A-3-=.a-6-diol), respectively. Intramolecular [2+2] photocyclization of this tricyclic diol afforded the corresponding cage diol, 3-methyl-7phenylpentacyclo[5.4.0.0 2 ,6 .03 , 1 0 .05, 9 ]undecane-.exogxa-8,11-diol. Oxidation of this cage diol with pyridinium chlorochromate in dry dichloromethane afforded a single, isomerically pure cage hydroxyketone, 3-methyl-7 phenylpentacyclo[5.4.02,6.03,l .1519]undecane-xA-8-ol-II-one, whose structure was established by single crystal X-ray crystallographic methods.
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Karlsson, Oskar. "Ferulic Acid – A Valuable Natural Compound for Sustainable Materials." Thesis, KTH, Skolan för kemi, bioteknologi och hälsa (CBH), 2020. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-290233.
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One of the largest problems that stands before us is the quest to find sustainable alternatives to fossil-based materials. Fossil-based products can be found all around us in our society. This quest has forced us to look for new ways to build materials. Synthetic polymer materials have traditionally been produced from fossil-based starting materials however, in modern times studies regarding biobased superseders for the unsustainable starting materials has been conducted. One of these new potential building blocks is ferulic acid (FA) that is an aromatic cinnamic acid. FA has previously been used as an antioxidant but since it in addition is aromatic, have more than two functional groups and contains a double bond between two carbons it holds a large potential for polymeric synthesis. FA has been isolated from agricultural side streams such as sugar beet pulp, flax shives, wheat- and corn bran through enzymatic release and pressurised low-polarity water extraction (PLPW). One of the largest areas of use regarding FA is the biological applications. It has been proven to be effective protection against UV-radiation which open up possible uses in the textile industry, cosmetics and skincare. FA has also shown biomedical properties such as antiallergic, anti-inflammatory, anti-diabetic, anticarcinogenic and antiviral properties among others. Two of the most common polymerization methods are free radical- and step-wise polymerization. FA shows great promise for the possibility to polymerize through both these methods since it has a double bond and more than two functional groups. Polymer materials produced from FA has been done with step-wise polymerization. The polymers showed thermostable and possibly biodegradable properties. Free-radical polymerization requires a monomer with a sterically unhindered double bond and for that reason the FA must be modified in order to polymerize using free radicals. This modified monomer has been produced in a small laboratory scale and can in theory be polymerized through radical polymerization.Ett av de största problemen som vi står inför i modern tid är hur vi ska ersätta material som är producerade från fossila bränslen. Dessa material finns överallt i vårt moderna samhälle och spelar en betydelserik roll i vår infrastruktur. Detta har tvingat oss att undersöka andra miljövänligare källor för att se om dessa kan ersätta de fossila. Polymera material är ett exempel på material som tidigare har haft en fossil bas. På grund av detta har dessa material och hur dem kan producerats undersökt för att se om det finns en alternativ biobaserad källa. Ferulsyra är en aromatisk kanelsyra som är mest känd för att ha antioxidatiova egenskaper. Utöver detta innehåller ferulsyra en dubbelbindning mellan två kol och dessutom fler än två funktionella grupper vilket indikerar att den kan vara en möjlig monomer för polymersyntes. Ferulsyra kan produceras från sidoströmmar från jordbruksindustrin så som till exemper sockerbetsmassa, linhår och vete, både genom enzymatiska reaktioner eller med hjälp av extraktion med ett lösningsmedel. En av de största användningsområdena gällande ferulsyra är inom biologiska applikationer. Den kan bland annat användas som solskydd, både inom hudvårdsindustrin och som ytbeläggning i textilier. Ferulsyra har också uppvisat medicinska egenskaper som visar på att det kan användas mot allergier, inflammationer, diabetes, canser och virussjukdomar. De två vanligaste metoderna för polymersyntes är fri radikalpolymerisation och stegvis polymerisation. Ferulsyra uppvisar stor potential för att kunna användas som monomer i båda metoderna då den innehåller en dubbelbindning mellan två kol och fler än två funktionella grupper. Syntes av ferulsyra genom stegvis polymerisation har genomförts. Resultatet var att de producerade materialen uppvisade termostabila och biologiskt nedbrytbara egenskaper. För att fri radikalpolymerisation ska vara möjligt med ferulsyra som monomer krävs det att dubbelbindningen inte är steriskt hindrad. Detta innebär att ferulsyra först måste modifieras innan polymerisationen är möjlig. Dessa modifieringar har genomförts på labbskala och den producerade monomeren är teoretiskt sätt möjlig att polymerisera genom fri radikalpolymerisation.
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Bertuzzi, Giulio. "Synthesis and functionalization of a lactam-pyrazole molecular scaffold as a promising anticancer compound." Master's thesis, Alma Mater Studiorum - Università di Bologna, 2015. http://amslaurea.unibo.it/9035/.
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The importance of pyrazole and lactam-based molecules in medical and pharmaceutical fields is underlined by the multitude of active ingredients on trade, such as Sildenafil or Apixaban, by Pfizer. In this work, a synthesis of an organic molecule with promising anticancer activity has been developed. This molecular scaffold is characterized by a δ-lactam-fused pyrazolic core, with a well-known biological activity and amenable of further functionalization. The synthetic strategy adopted for the obtainment of the core was based on a 1,3-dipolar cycloaddition of a nitrilimine with an α,β-unsaturated δ-lactam. Secondly, in order to give the final compound an elevated pharmacological activity, a functionalization with a double “side chain”, namely molecular fragment able to improve the interaction with particular biological receptors, was achieved. The target compound was thus obtained, with a highly convergent synthesis, and will be tested for antiproliferative activities towards different cellular lines.
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Hagey, H. Louis. "Compound catalyst for the production of C¦1-C¦4 hydrocarbons from synthesis gas." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1997. http://www.collectionscanada.ca/obj/s4/f2/dsk2/ftp04/mq21065.pdf.
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Wu, Hanxiang. "Amino acid and glucose conjugates of a phenylpyrrole compound : synthesis, systemicity and biological properties." Thesis, Poitiers, 2017. http://www.theses.fr/2017POIT2261/document.
Full textAbstract:
Le but de notre travail est de développer une stratégie de vectorisation pour conférer la mobilité phloémienne aux produits agrochimiques en appliquant le concept de prodrogue dans l'élaboration de composés phytopharmaceutiques. Le fenpiclonil, fongicide non systémique de la famille des phénylpyrroles, a été choisi comme composé parent modèle et modifié en l'associant à un acide alpha-aminé ou à un monosaccharide.La mobilité phloémienne des conjugués entre le fenpiclonil et les acides L ou D-glutamique ou le D-glucose (D-GFC) a été évaluée chez des plantules de ricin. Le test de systémie a montré que le L-aminoacide était nettement plus favorable à la mobilité phloémienne que l'acide D-aminé ou le D-glucose. Les résultats suggèrent que le conjugué fenpiclonil/L-aminoacide est reconnu et manipulé par un système de transport d'acide aminé stéréospécifique énergisé par la force proton-motrice. Des expériences complémentaires ont montré que le D-GFC était un inhibiteur puissant et sélectif de l'absorption du saccharose par les tissus foliaires et du chargement phloémien du saccharose. En raison de l'inhibition spécifique des transporteurs de saccharose (par exemple AtSUC2), le D-GFC peut être envisagé comme un nouvel outil en phloémologie.Enfin, nous avons exploré l'impact de la modification de structure de l'espaceur afin d'optimiser la stratégie de prodrogue. Après avoir introduit différentes structures d'espaceur entre le fenpiclonil et la fonction acide aminé, le conjugué qui contient un cycle triazole avec l'acide aminé comprenant la chaine la plus courte a montré la meilleure mobilité phloémienne et, par ailleurs, une systémie optimisée par rapport aux dérivés acides du fenpiclonil dans la gamme des valeurs de pH de l'apoplasme foliaireThe purpose of our work is to develop a vectorization strategy to confer phloem mobility to agrochemicals by applying prodrug concept into agrochemical design. Fenpiclonil, a non-systemic fungicide from the phenylpyrrole family, was selected as a model parent compound and modified by associating it with an amino acid or a monosaccharide.The phloem mobility of L and D-glutamic acid and D-glucose fenpiclonil conjugates (D-GFC) was evaluated in Ricinus seedlings. The systemicity test showed that the L-amino acid promoiety was clearly more favorable to phloem mobility than D-amino acid or D-glucose. The results suggested that the transport of the L-amino acid conjugate is governed by a stereospecific amino acid carrier system energized by the proton motive force. Further investigation indicated that D-GFC was a potent and selective inhibitor of sucrose uptake by leaf tissues and sucrose phloem loading. Due to its specific inhibition of sucrose transporters (e.g. AtSUC2), D-GFC can be a candidate as a new tool in phloemology. Finally, we explored structural modifications of the spacer arm to optimize the prodrug strategy. Different structures of the spacer arm were introduced between fenpiclonil and the amino acid function. The conjugate which contains a triazole ring with the shortest amino acid chain showed the best phloem mobility and a better systemicity than fenpiclonil acidic derivatives within the pH range of the foliar apoplast
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Li, Maohua. "Synthesis of Polyketones from Zwitterionic Nickel Compound Catalyzed Copolymerization of Carbon Monoxide And Olefins." University of Akron / OhioLINK, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=akron1461772542.
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Numbere, Macba Giolda. "Methodologies for the synthesis of compound 48/80 analogues as modulators of P13K and PKB." Thesis, University College London (University of London), 2008. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.498562.
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Folmar, Michele L. "Synthesis and Characterization of a New Ruthenium(II) Polypyridyl Compound with a Quinolate-Type Ligand." The Ohio State University, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=osu1469047981.
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Mashni, Jamil Assad. "DEVELOPMENTS IN SIGNAL AMPLIFICATION BY REVERSIBLE EXCHANGE (SABRE) OF 15N AND 13C NUCLEI TOWARDS APPLICATIONS IN MRI." OpenSIUC, 2019. https://opensiuc.lib.siu.edu/theses/2516.
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Signal Amplification by Reversible Exchange (SABRE) is a hyperpolarization technique that utilizes parahydrogen for the NMR signal enhancement of nuclear spins. SABRE is related to Parahydrogen Induced Polarization (PHIP), another means of hyperpolarization using parahydrogen; PHIP achieves hyperpolarization via chemical reduction. Although PHIP and SABRE share many similarities in experimentation, PHIP ultimately requires the presence of an unsaturated chemical bond as well as pairwise-addition of parahydrogen. No permanent chemical change occurs during SABRE, and instead may be considered as a merely physical exchange between molecules with sites on a catalyst. PHIP and SABRE may be compared to Dynamic Nuclear Polarization (DNP), arguably the most well-known and researched method for hyperpolarization; despite all that has been achieved with DNP, PHIP and SABRE offer vastly more-rapid, less-expensive, and more-simplified approaches for achieving hyperpolarization. The focus of this work is experimentation with SABRE processes and methods designed to overcome certain experimental challenges associated with this technique.
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陳淑恆 and Suk-hang Chan. "Synthesis of diazacrown ether and transition metal containing polymersby atom transfer radical polymerization and other methods." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2002. http://hub.hku.hk/bib/B3124287X.
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Chen, Yu-Feng, and 陳郁丰. "Reductive Dimerization of Nitroso Benzene Compounds: Synthesis of Symmetrical Azoxybenzenes." Thesis, 2016. http://ndltd.ncl.edu.tw/handle/03444909598063710870.
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碩士中原大學
化學研究所
104
In this thesis, we used the reductive dimerization to synthesize azoxybenzenes from nitroso benzenes. The reaction was found to be influenced by oxidants, and steric hinder of substitutions in aromatic rings, when primary aromatic amines oxidized to nitroso benzenes. We successfully synthesized nitroso benzenes as substrates including 1a-1q by oxidants , such as Oxone®, and hydrogen peroxide. Using the nitroso benzenes as starting material, we synthesized the azoxybenzenes 2a-2s simple by heating at 100 oC in IPA, and we found that the the reaction concentration and the reaction time affected the yield of the azoxybenzenes. Without the usage of other reagents, our experimental procedure is simple, and capable of synthesizing a wide variey of azoxybenzenes.
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Lundmark, Penelope J. "Synthesis, characterization and reactivity of Group 6 alkoxo nitrosyl complexes." Thesis, 1993. http://hdl.handle.net/2429/1832.
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Three new classes of alkoxo nitrosyl complexes of the type Cp*M(NO)(OR)X (Cp* =C5Me5; M = Mo, W; R = alkyl, aryl; X = CI, OR, alkyl), all of which have been fully characterized, are prepared by metathesis reactions. The molecular structures ofCp*W(NO)(OCMe3)2 and Cp*W(NO)(OCH2Ph)2 have been established by X-ray crystallographic analyses. While in general the above metathesis reactions are straightforward, two interesting bimetallic complexes, [Cp*W(N0)(CH2SiMe3)][Cp*W(C1)(0)]-(112-il:T12-NC(H)SiMe3) and [Cp*W(N0)(CH2SiMe3)C1][Cp*W(C1)(i2-N{0){H)CH2SiMe3)]-(1.t-N), are produced in attempts to prepare alkoxo alkyl complexes using potassium salts. X-ray crystallographic analyses of both products are presented. The reaction chemistry of the three classes of alkoxo complexes, Cp*M(NO)(OR)X, with a variety of reagents such as oxygen, water, phosphines, carbon monoxide, dihydrogen, HCI, isonitriles and isocyanates has been investigated. In general, the 18-electron bis(alkoxo)complexes are chemically inert to most of these reagents; the only exceptions being the reactions of Cp*M(NO)(OR)2 with H2 and HC1. The inertness of the bis(alkoxo) complexes is attributed to donation of electron density from filled p-type orbitals on the oxygen atoms into empty metal orbitals on the metal center. The reactivity studies of the chloro compounds are limited because of their extreme air- and moisture-sensitivity. In contrast, the alkoxo alkyl complexes decompose cleanly to isolable organometallic species when treated with 02 or H2O. In Lewis acid-base type reactions with PMe3, CNCMe3, PhNCO and p-tolylNCO, the Cp*M(N0)(R)(OR') species have sufficiently electron-deficient metal centers to form 1:1 adducts and/or insertion products. The diamagnetic bimetallic complex, [Cp*Mo(N0)(CH2Ph)(11-0)]2, is produced when Cp*Mo(NO)(CH2Ph)(OCMe3) is treated with H2 in THF. Earlier work into the reactions of dialkyl complexes, Cp'W(NO)R2 (Cp' = r15-05H5, is-C5Me5), with carbon monoxide has been extended to permit some general conclusions regarding CO-insertion reactions in these systems. These studies show that the products obtained from the carbonylation of various Cp'W(NO)R2 complexes are very dependent upon the nature of the ancillary ligands. The nature of the cyclopentadienyl ligand determines the extent of the reactivity, with only the Cp complexes inserting a second equivalent of CO. The nature of the hydrocarbyl group influences the rate of the reaction such that the greater Lewis acidity of the diaryl complexes results in their forming monoacyl products faster than do the related dialkyl complexes. However, only the monoacyl alkyl complexes possess a sufficiently weak M-C bond to undergo a second insertion of CO to form bis(acyl) species, Cp'W(NO)(C{O}R)2. The nature of the hydrocarbyl ligand also plays an influential role in the case when R = CH2Ar in that putative reductive elimination of ketone occurs from the undetectable monoacyl intermediate complexes.
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Sharp, William Brett. "Synthesis and ligand reactivity of group 6 organometallic nitrosyl complexe." Thesis, 2001. http://hdl.handle.net/2429/13416.
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Reaction of Cp*WR₂(NO) (R = CH₂SiMe₃ , CH₂Ph) complexes with HBF₄ yields the nitrosyl-borane adduct species Cp*WR₂ (NOBF₃) via degradation of the tetrafluoroborate counterion. The similar materials, Cp*WR₂(NOB(C₆F₅)₃), can be prepared by the addition of perfluorophenylborane to the metallonitrosyl complex. The reaction of a protic acid containing a very weakly coordinating anion ([H(OEt₂)₂][B(3,5-(CF₃)C₆H₃)₄]) with the tungsten nitrosyl species yields the first complexes containing a terminal hydroxylimido ligand, [Cp*WR₂ (NOH)]⁺. These complexes have been characterised by single crystal X-ray crystallography, and their solution behaviour has been studied by NMR spectroscopy. The dimethyl complexes, Cp*MoMe₂ (NO), have proven to be remarkably elusive synthetic targets in our laboratories. Thus, treatment of [Cp*MoCl(NO)(μ-Cl)]₂ with magnesium (Me₂Mg-dioxane, MeMgCl) or aluminum (Me₃Al) based methylating reagents leads only to metathesis of a single chloro ligand and the formation of the known compound [Cp*MoMe(NO)(μ-Cl)]₂. Similar treatment of the dichloro precursor with MeLi in ethereal solvents generates an equimolar mixture of the mono(methyl) complex and the trimethyl 'ate' complex, Cp*MoMe₃(NO-Li(OEt₂)[sub n]). In toluene at low temperatures, MeLi can be utilised to effect complete metathesis of the chloro ligands of [Cp*MoCl(NO)(μ-Cl)]₂ and generate the target dimethyl complex, Cp*MoMe₂(NO), in high yield. In solution this compound is predominantly a monomeric species similar to its more sterically encumbered congeners, whereas in the solid state it adopts a dimeric or oligomeric structure containing isonitrosyl bridges as indicated by IR and solid-state NMR spectroscopies. The reaction of the dimethyl complex with a range of Lewis bases, L, to form the 18e adducts Cp*MoMe₂L(NO), has established it to be the most electrophilic complex of its family. Most interestingly, the dimethyl complex is thermally unstable in solution and undergoes an (R-)[M](-NO) to (0=)[M](=NR) isomerisation to its oxo imido form, Cp*Mo(NMe)(O)Me, which is isolable from the final reaction mixture as the μ-oxo bridged adduct Cp*Mo(NO)Me₂(μ-O)Cp*Mo(NMe)Me. The rate of this isomerisation is significantly faster for the tungsten dimethyl complex; hence Cp*WMe₂(NO) is not isolable free of a supporting donor interaction. Under mild thermolysis conditions the tungsten complexes CpW(o-tolyl)₂(NO) undergo an aryl group isomerisation to form the mixed o-tolyl p-tolyl and o-tolyl m-tolyl complexes. The overall in-plane rotation of the tolyl group occurs via an η²-toluene η²-toluyne intermediate.
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Ma, Cheuk-Ki. "Synthesis and stereochemical investigation of the redox-active iron-chalcogenide nitrosyl clusters." 1992. http://catalog.hathitrust.org/api/volumes/oclc/28159039.html.
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Thesis (Ph. D.)--University of Wisconsin--Madison, 1992.Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.
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黃郁仁. "The Synthesis and Studies of Azo Compound." Thesis, 1995. http://ndltd.ncl.edu.tw/handle/46011789994570079601.
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碩士國立成功大學
化學學系
83
The content of this thesis is majorly divided into two parts. In the first part, the influences of the electrode mate-rials (PbO2、 PtOX、 PdOX、 NiCo2O4 (Ru+Ir)O2 and graphite), acetonitrile/ water ratio. OH- concentration, and anolyte temperature on the anodic synthesis of 4,4'-dinitroazobenzene from p-nitroaniline were investigated by voltammetric and electrolytic method. The usage of PbO2 and increase in acetonitrile/water ratio increase the current efficiency (C.E.) of this reaction due to the inhibition for a poisoning layer formed on the electrode surface from the products/residues of the p-nitroaniline. A suitable control of the OH- concen- tration in the anolyte optimizes. the C.E. of this reation since O2 evolution rate is more sensitive to pH values of anolyte than that of 4,4'-dinitroazobenzene formation. The C.E. of the 4,4'-dinitroazobenzene formation is independent of solu-tion temperature, implying that this reation is controlled by the electron transfer from p-nitroaniline to electrode but not chemical coupling of the NO2C8H4NH. radicals. In the second part, diazotised 3-(aminophenyl)sydnones may be coupled with phenol derivatives or naphthol derivatives in alkaline solution to synthesize new azo compounds containing sydnonyl group.
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Li, Chien-Hung, and 黎建宏. "Synthesis of serine cyclopeptide based cage compound." Thesis, 2013. http://ndltd.ncl.edu.tw/handle/68433492226592557004.
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Hsieh, Chung-Hung, and 謝忠宏. "Iron-Thiolate Nitrosyl Complexes: Synthesis, Reactivity andApplication of the Biomimetic Dinitrosyl Iron Complexes." Thesis, 2008. http://ndltd.ncl.edu.tw/handle/65349167459218627947.
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博士國立清華大學
化學系
96
Addition of the stronger -donating and -accepting phosphine ligands, PPh3, PPh3-3-SO3Na or Ph2P(CH2)5PPh2, triggered the reductive elimination of bridged thiolates of RRE [Fe(μ-SC6H4-o-COOH)(NO)2]2 (1) to yield the EPR-silent neutral {Fe(NO)2}10 [(PPh3)2Fe(NO)2] (2), the water-soluble {Fe(NO)2}10 [(PPh3-3-SO3Na)2Fe(NO)2] (4), and the dimeric {Fe(NO)2}10-{Fe(NO)2}10 DNICs [Fe2(-μ-PPh2(CH2)5PPh2-)2(NO)4] (3), respectively. Complex 2-4 were characterized by IR, UV-vis, and single-crystal X-ray diffraction. Oxidation of complex 3 by 2 equiv of [NO][BF4] resulted in the formation of EPR-active cationic {Fe(NO)2}9-{Fe(NO)2}9 dimeric complex [Fe2(-μ-PPh2(CH2)5PPh2-)2(NO)4][BF4]2 (32+). Reaction of complex 32+ with thiolates ([PPN][SC7H4SN], [PPN][SPh] or [PPN][SEt]) yields anionic {Fe(NO)2}9 complex [PPN][(SC7H4SN)2Fe(NO)2] (6) and neutral {Fe(NO)2}10 complex 3. These results unambiguously illustrate one aspect of how the reducing ability and the binding mode of the thiolate ligands functions to regulate the conversion of cationic {Fe(NO)2}9 into anionic {Fe(NO)2}9 or neutral {Fe(NO)2}10 DNICs upon the reaction of complex 32+ and thiolates. Dimeric {Fe(NO)2}9 dinitrosyl iron complex (DNIC) [Fe(μ-SC7H4SN)(NO)2]2 (5) with S and N atoms of the anionic [-SC7H4SN-]– ligand bound to two separate {Fe(NO)2}9 cores, respectively, shows the Fe…Fe distance of 4.0 Å. A straightforward reaction of complex 5 and nucleophiles (PMe3, imidazole, [PhCOO]-, [OPh]-, [SC7H4SN]- or [N3]-) led to the EPR-active {Fe(NO)2}9 DNICs in THF. In addition, the precursor [(CO)2Fe(NO)2][BF4] (12) provided a new method for synthesizing several kinds of DNICs with different ligations, such as [(SC5H5N)2Fe(NO)2]- (13), [(NO2)2Fe(NO)2]- (15), [(NO3)2Fe(NO)2]- and [(OPh)2Fe(NO)2]- (16). All these {Fe(NO)2}9 DNICs can be classified into the anionic {Fe(NO)2}9 DNICs with S/N/O ligation, the neutral {Fe(NO)2}9 DNIC with one thiolate and one neutral imidazole ligation, and the cationic {Fe(NO)2}9 DNICs with the neutral P-containing coordinated ligands. Moreover, the biotinylated ligand, N,N'-[dithiobis(4,1-phenylene)]bis{5-[(3aS,6aR)-2-oxohexa-hydro-1H-thieno[3,4-d]imidazol-4-yl]pentanamide} ([(SC6H4-o-NHCO(CH2)4Biotin)2]; Ligand 1) and biotinylated RRE [Fe(μ-SC6H4-o-NHCO(CH2)4Biotin)(NO)2]2 (17) were synthesized and identified by NMR, IR, UV-vis. EA and ESI-MS. The HABA assay shows that the average 3.19 (Ligand 1) and 3.64 (complex 17) biotinylated parts bind to avidin. The water-soluble iron-thiolate NO trapping agent/scavenger [Na•3THF][Fe(SC6H4-o-S)2]2 (18) was synthesized and characterized. Reaction of complex 18 and [PPN][Cl] resulted in the formation of [PPN]2[Fe(SC6H4-o-S)2]2 (20) via cation exchange. Nitrosylation and the subsequent sulfur oxygenation of complex 20 yielded the dimeric disulfinate {Fe(NO)}6 complex [PPN]2[(NO)Fe(SO2C6H4-o-SO2)(μ-SC6H4-o-S)]2 (25). Reduction of complex 25 by [PPN][SC6H4-o-NH2] resulted in the formation of {Fe(NO)}7 complex [PPN]2[(NO)Fe(SO2C6H4-o-SO2)(SC6H4-o-S)] (26) with a bent Fe-N-O bond angle of 165.7o. Complex 20 was adopted as the precursor to synthesize complexes [PPN][(Cl)Fe(S-C6H4-o-S)(S,SCN(CH3)2)] (27), [(NO)Fe(S-C6H4-o-S)(S,SCN(CH3)2)] (30) and [PPN][(NO)Fe(S-C6H4-o-S)(S, SCN(CH3)2)] (31) with mixed [S-C6H4-o-S]2- and [S,SCN(CH3)2]- coordinated ligands. Nitrosylation of complex 27 led to the formation of complex 30. Photolysis of complex 30 in the presence of [PPN][Cl] led to the formation of complex 27. Reduction of {Fe(NO)}6 complex 30 by [PPN][SPh] resulted in the formation of {Fe(NO)}7 complex 31 with a bent Fe-N-O bond angle of 150.8o. Upon addition of O2 into a CH2Cl2 solution of complex 30 or 31, respectively, the yellow decomposition occurred for complex 30, while, complex 30 was reobtained from O2 oxidation of complex 31. Obviously, the deficient electronic density surrounding the iron center resulting form the less electron-donating anionic dithiocarbamate ligand retards the sulfur oxygenation of 1,2-benzenedithiolate to yield the iron-thiolate sulfinate nitrosyl complex. Moreover, the solvent dependent complexes 18 and 20 can convert acetonenitrile to acetamide in the presence of NaOH. This result implicates that the substrate nitrile coordinating to the catalytic metal center of active site is a key step of nitrile hydrolysis to amide. In the animal model studies, the aqueous solution of complex 18 was injected to the right femoral vein as the NO trapping agent/scavenger to male Wistar rats, which increased the blood pressure around 10 mmHg. The neutral trinuclear iron-thiolate nitrosyl, [(ON)Fe(μ-S,S-C6H4)]3 (23), and its oxidation product, [(ON)Fe(μ-S,S-C6H4)]3[PF6] (24), were synthesized and characterized by IR, X-ray diffraction, X-ray absorption, EPR and magnetic measurement. The five-coordinated square pyramidal geometry around each iron atom in complex 23 remains intact when complex 23 is oxidized to yield complex 24. Magnetic measurements and EPR results show that there is only one unpaired electron in complex 23 (Stotal = 1/2) and no unpaired electron (Stotal = 0) in 24. The detailed geometric comparisons between complexes 23 and 24 provide the understanding of the role that the unpaired electron plays in the chemical bonding of this trinuclear complex. Significant shortening of the Fe-Fe, Fe-N and Fe-S distances around Fe(1) is observed when complex 23 is oxidized to 24. This result implicates that the removal of the unpaired electron does induce the strengthening of the Fe-Fe, Fe-N and Fe-S bonds in Fe(1) fragment. A significant shift of the NO stretching frequency from 1751 cm-1 (23) to 1821, 1857 cm-1 (24) (KBr) also indicates the strengthening of the N-O bonds in complex 24. The EPR, X-ray absorption and magnetic measurements lead to the conclusion that the unpaired electron in complex 23 is mainly allocated in Fe(1) fragment and was best described as {Fe(1)NO}7.
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Veltheer, John E. "Synthesis and characteristic chemistry of sixteen-electron group 6 hydrocarbyl-containing nitrosyl complexes." Thesis, 1993. http://hdl.handle.net/2429/2202.
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This thesis addresses the non-generality of the previous method used to prepare CpW(NO)(alkyl)2 complexes from their diiodide precursors. The three most significant problems inherent to the original synthetic method were: (a) the reagents being used (i.e. transition-metal dihalide, alkylating agent and solvent), (b) excessive hydrolysis during workup, and (c) thermal decomposition. This work presents a rationalization for, and utilization of, a new general methodology for the preparation of Cp'M(NO)R2 [Cp' = Cp (i5-05H5), Cp* (i5-05Me5);
M = Mo, W; R = alkyl, aryl] complexes. Reactions of Cp*M(NO)C12 with (ary1)2Mg•X(dioxane) [aryl = Ph, p-tolyl, o-tolyl] in THE provide Cp*M(NO)(aryl)2 complexes. These 16-electron diaryl complexes irreversibly form 1:1metal-centered adducts with PMe3. CpW(NO)(o-tolyl)2 is the only isolable diaryl complex of this type that does not incorporate a Cp* ligand. Electrochemical and IR studies indicate that the sediaryl complexes are more potent Lewis acids than their Cp'M(NO)(alkyl)2 congeners. X-raycrystallographic analyses indicate that these diaryl complexes have more sterically accessible metal centers than related dialkyl complexes. The thermal stability of Cp'M (NO)R2 complexes is Cp* >Cp, W > Mo and alkyl > aryl. The relative Lewis acidities of this family of nitrosyl complexes mirrors the thermal stability trend. Reactions of Cp*Mo(NO)C12 with (alky1)2Mg•X(dioxane) [alkyl = CH2CMe3, CH2CMe2Ph,CH2SiMe3] in THE provide previously inaccessible Cp*Mo(NO)(alkyl)C! and Cp*Mo(N0)(alky1)2 complexes in a stepwise fashion. Cp*Mo(NO)(alkyl)Cl species are comparable in Lewis acidity to related Cp*Mo(N0)(ary1)2 complexes. Cp*Mo(NO)(CH2CMe3)Cl reacts with PMe3 and pyridine to afford metal-centered 18-electronadducts while CO and CNCMe3 readily insert into its Mo-neopentyl bond. The chloride ligand inCp*Mo(NO)(CH2CMe3)Cl is easily abstracted by Ag+ in NCMe to form[Cp*Mo(NO)(CH2CMe3)(NCMe)]BF4. The phosphine complex, Cp*Mo(N0)(CH2CMe3)(PMe3)C1, is readily dehydrohalogenated by LDA in THE to afford the novel cyclometallated dialkyl complex (15,111-05Me4CH2)Mo(N0)(CH2CMe3)(PMe3). Reactions of Cp*Mo(NO)R2 complexes with water afford bimetallic complexes of the type,[Cp*Mo(NO)R]2-(11-0), and free hydrocarbon. A kinetic analysis of the reaction between H2Oand Cp*Mo(N0)(CH2SiMe3)2 implicates Cp*Mo(NO)(CH2SiMe3)(OH) as a key intermediate in the formation of [Cp*Mo(N0)(CH2SiMe3)]2-(A-0). Cp'W(NO)(alkyl)2 complexes are hydrolytically stable, whereas Cp'W(NO)(aryl)2 complexes react vigorously with water providing Cp'W(0)2(aryl) complexes. CpMo(NO)(CH2CMe3)2 thermally decomposes via a first-order intramolecular extrusion of neopentane yielding the 16-electron alkylidene complex, CpMo(NO)(=CHCMe3). A mechanistic analysis of the above-mentioned thermal reaction shows little solvent dependence and suggests a highly ordered transition state. CpMo(NO)(=CHCMe3) cannot be isolated, but it can be trapped with phosphines or pyridine (L) yielding CpMo(NO)(=CHCMe3)L complexes. Primary amines and alcohols add their heteroatom-hydrogen bonds across the Mo=C double bond of CpMo(NO)(=CHCMe3) stereoselectively to give alkyl amide and alkyl alkoxide complexes. CpMo(NO)(=CHCMe3) reacts with CpMo(NO)(CH2CMe3)2 to give [CpMo(NO)](12-11 1:112-N0)(A-CHCMe3)[CpMo(=CHCMe3)], which contains the first g-111:12-nitrosyl ligand.
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Yueh-E, Shih, and 施月娥. "Synthesis and Characterization of Diiron Complexes containing a Phosphido Bridge and a Nitrosyl Ligand." Thesis, 1993. http://ndltd.ncl.edu.tw/handle/72754580906329127865.
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黃虹淵. "Synthesis and Evaluation of Fluoroquinolone Compound Against M.Tuberculosis." Thesis, 2003. http://ndltd.ncl.edu.tw/handle/45471394158300704445.
Full textAbstract:
碩士高雄醫學大學
化學系碩士班
91
Abstract Several of the fluoroquinolone antibacterial agents, such as norfloxacin, ofloxacin, ciprofloxacin, and temafloxacin, have been examined as potential chemotherapeutics for Mycobacterium tuberculosis infection. These fluoroquinolones show good penetration into macrophages where they are both concentrated and retain a high degree of activity. This property is particularly important since it is well-known that surface-associated lipids of mycobacteria form a transport barrier when compared to the cell wall of true bacteria. In our studies to discover new anti-TB agents, numerous fluoroquinolones, bearing 5-substiuted-pyran-4-one, 3-substiuted-pyridin- 4-one, and aryl- or heteroaryl-hydrazone, were synthesized and evaluated for anti-TB activities. Among the fluoroquinolones were screened against H37Rv at a sample concentration of 6.25μg/mL by the Tuberculosis Antimicrobial Acquisition and Coordinating Facility (TAACF). Among the N-(5-benzyloxy-4-oxo-4H-pyran-2-ylmethoxy)-fluoroquinolones 14a-d demonstrated >50% inhibitory activity and the remaining test compounds were inactive or weakly active.
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Chen, Chyi-Lin, and 陳祺霖. "Synthesis and Study of ESIPT And ESDPT Compound." Thesis, 2011. http://ndltd.ncl.edu.tw/handle/89021033325648943253.
Full textAbstract:
博士國立臺灣大學
化學研究所
99
The dual function of the excited-state intramolecular proton transfer (ESIPT) in the newly synthesized 3-hydroxy-2-(pyridin-2-yl)-4H-chromen-4-one has been recognized. One of the two ESIPT routes typically happens between the hydroxyl group and the carbonyl group in a five-membered ring configuration. The other occurs between the hydroxyl group and the pyridinic group in a six-membered ring configuration. The switchable ESIPT implies the potential applications of the pH fluorescent indicator and the anion chemosensor. The dual function in the 3-hydroxyflavone derivative is believed to further spark large interests for the utilization of the ESIPT in a more practical way. On the other hand, the ESPT dyanmcis via intermolecular hydrogen bonding has also been reviewed. Particually, a four 6HIQ is strategically designed and synthesized; it possesses a central moiety of 7-azaindole (7AI) and undergoes excited-state double proton transfer (ESDPT). Despite a barrierless type of ESDPT in the 6HIQ dimer, femtosecond dynamics and a kinetic isotope effect provide indications for a stepwise ESDPT process in the 6HIQ/7AI heterodimer.
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Yang, Yu Li, and 楊聿理. "Synthesis and reactivity of methylene-bridged tungsten compound." Thesis, 1996. http://ndltd.ncl.edu.tw/handle/hzht3q.
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Wang, Yi-Chi, and 王藝琦. "Bismuth Titanate Compound: Synthesis, Characterization and Photocatalytic Applications." Thesis, 2016. http://ndltd.ncl.edu.tw/handle/38177409062803661059.
Full textAbstract:
碩士國立中興大學
化學工程學系所
104
The preparetion of photocatalyst Bismuth Titanate compound has been synthesized by the combination of direct hydrolysis method and hydrothermal treatment. The investigated parameters include molar ratio of Bi:Ti, hydrothermal temperature, and hydrothermal time. The photocatalytic reaction efficiency and the adsorption of dark box were used to determine the best conditions for the preparation of bismuth titanate photocatalyst. The structural information and morphology of the nanoparticles Bismuth Titanate compound were characterized by BET、XRD、TGA、FTIR、SEM/TEM、EDS、ICP、ESCA and UV-visble spectroscopy. In this study, the bismuth titanate photocatalyst was investigated by the photodegradation of methyl orange under the irradiation of UV light, and no light adsorption experiments (dark box adsorption). The degradation results of the methyl orange and dark box adsorption indicate that the best conditions of the preparation of bismuth titanate are the Bi : Ti molar ratio of 1:1, the hydrothermal temperature of 200°C, and the hydrothermal time for 12h, and can reach the best photocatalytic activity and the degradation rate of 48 %.