Instrumenteringens klangfärg inom rörliga bilder erhåller en viktig funktionalitet då musikaliskt berättande oftast vilja återskapa känslor som speglar berättelsen främst. Det är därför som kandidatuppsatsen avser gå in närmare på området och detta för att bidra med mer kunskap. Gällande urvalet har denna gjorts på filmmusik komponerad av James Horner där en selektion varit på sammanlagt sex filmer med totalt tre regissörer. För att kunna utföra undersökningen därav besvara frågeställningarna har metoden varit innehållsanalys där resultat visar på likheter inom den instrumentation som används. Förutom detta finnas undantag, men att instrumenteringen då möjligtvis vara där för ett hastigt beslut. Bortsett från vad som benämnts behandlar uppsatsens teori samt tidigare forskning musikvetenskap, men även kompositionslära samt musikpsykologi.

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The aim of this bachelor thesis was to examine how news journalism represented the two swedish journalists Kim Wall and Nils Horner, when describing their posthumous reputation after they were murdered during assignments. The research questions examined were: How does the journalism, in describing their posthumous reputations, portray the story of Kim Wall, and Nils Horner? What differences and similarities can be found in how they are portrayed as journalists, and as victims? We used Faircloughs critical discourse analysis (CDA) to find reoccurring discourses in the description of Horner and Wall. By examining the characteristics they were assigned and what conclusions the audience were offered to draw about their journalistic competence and about them as victims of murder, we found many similarities between Horner and Wall. They are both described as exceptionally competent. They are also portrayed as born with a “calling” towards the journalistic profession, and in both cases, they are ascribed with next to supernatural characteristics. As victims of murder we found them to be portrayed as idealistic, with some variations in relation to the description of the content of their character, and where the murder took place. Our study shows that the discourses we found contribute to the creation of heroic myths in the news journalisms description of them. They are elevated, and our conclusion is that by elevating their murdered colleagues as heroes, the news journalists are also elevating themselves and, in turn, the journalistic profession.

In the Introduction part of this thesis, the chemistry of organofluorine compounds is discussed, particularly the methods for the preparation of organofluorine compounds mainly by fluoroalkylation methods. Furthermore, the chemistry of fluorinated phosphonates, methods of their preparation, reactivity and biological activity is discussed. Additionally, the reactivity of fluoromethane derivatives is briefly mentioned and especially, the reactivity of diethyl fluoromalonate and fluorobisfenylsulfonylmethane is described. The Results and discussion part is devoted to the reactivity of three fluorinated phosphonates: tetraethyl fluoromethylenbisphosphonate, diethyl fluorophenylsulfonylphosphonate and previously not described diethyl fluoronitromethylphosphonate. These fluorinated phosphonates belong to the family of nucleophilic monofluoroalkylation reagents, meaning that these compounds are convenient starting materials for the synthesis of complex organic molecules containing the fluorine atom. The results deal with the reactivity of above mentioned fluorinated phosphonates, mainly with alkylation reactions, Horner-Wadsworth-Emmons reactions and conjugated additions. Also, other synthetic methods such as the Mitsunobu reaction or the palladium catalyzed allylation reaction were investigated; however,...

Conselho Nacional de Desenvolvimento Científico e Tecnológico / This paper presents the Horner-Wadsworth-Emmons olefination applied to preparing 22 new 5-alkoxy-3-trifluoromethyl-penta-2,4-dienenitriles (5), 5- phenylthio-3-trifluoromethyl-penta-2,4-dienenitriles (6) and ethyl 4-alkoxy-2- cyanomethylene-but-3-enoates (7) from the condensation between diethyl cyanomethylphosphonate (4) and β-alkoxyvinyl ketones (1), β-phenyltiovinyl ketones (2) and ethyl 4-alkoxy-2-oxo-but-3-enoates (3), furnishing the desired products with 10 to 93% yields. In a second step, this paper presents a simple and accessible novel synthetic route, for the preparation of a series of 30 unpublished 1,6- disubstituted 4-trifluoromethyl-pyridin-2(1H)-imines (14-19) from the condensation reaction of 5-aryl-3-trifluoromethyl-5-methoxy-penta-2,4- dienenitriles (Ar = Ph, 4-F-C6H4, 4-Br-C6H4, 4-Me-C6H4 and 4-MeO-C6H4) (5) with primary amines R-NH2 (R = Bu, 2-(1-cyclehexenil)ethyl, 2-(4- morpholinyl)ethyl, 2-phenethyl-ethyl, 2-(4-chlorophenethyl)ethyl and 2-(4- methoxyphenethyl)ethyl) (8-13), in a solvent free sealed system to give the expected products with yields between 20 to 98%. In addition, a series of new 6-substituted 4-trifluoromethyl-2H-pyran-2- ones (20) was obtained in 88 to 100% yeld, from the autocondensation reaction of 5-aryl-3-trifluoromethyl-5-methoxy-penta-2,4-dienenitriles (Ar = Ph, 4-F-C6H4, 4-Br-C6H4, 4-Me-C6H4 and 4-MeO-C6H4) (5), in a reflux system using water as solvent in the presence of HCl and 1 equivalent of ZnBr2. The pyridinimines, pyranones and dienes obtained in this work were identified and characterized by Hydrogen Nuclear Magnetic Resonance (H1NMR), Carbon-13 Nuclear Magnetic Resonance (C13 NMR), Mass Spectroscopy (GC-MS-EI), High Resolution Mass Spectroscopy (HRMS-ESI) and Elemental Analysis. / Este trabalho apresenta a metodologia de olefinação Horner-Wadsworth- Emmons aplicada de maneira inédita na preparação de 22 novas 5-alcóxi-3- trifluormetil-penta-2,4-dienonitrilas (5), 5-feniltio-3-trifluormetil-penta-2,4- dienonitrilas (6) e 4-alcóxi-2-cianometileno-but-3-enoato de etila (7) a partir da reação entre cianometilfosfonato de dietila (4) e respectivas β-alcoxivinil cetonas (1), β-feniltiovinil cetonas (2) e 4-alcóxi-2-oxo-but-3-enoatos de etila (3), levando a formação dos produtos com rendimentos entre 10 e 93%. Numa segunda etapa, este trabalho apresenta uma nova rota sintética, simples e acessível, para a preparação de uma série de 30 inéditas 4- trifluormetil-piridin-2(1H)-iminas 1,6-dissubstituídas (14-19) a partir da reação de condensação entre os 5-aril-3-trifluormetil-5-metóxi-penta-2,4-dienonitrilas (Ar = Ph, 4-F-C6H4, 4-Br-C6H4, 4-Me-C6H4 e 4-MeO-C6H4) (5) com aminas primárias R-NH2 (R = Bu, 2-(1-cicloexenil)etila, 2-(4-morfolinil)etila, 2-fenetiletila, 2-(4-clorofenetil)etila e 2-(4-metoxifenetil)etila) (8-12), em um sistema fechado e sem solvente, obtendo os produtos esperados com rendimentos de entre 20 e 98%. Em outra etapa do trabalho, foram obtidas 4-trifluormetil-2H-piran-2-onas 6-substituídas (20) a partir da reação autocondensação de 5-aril-3-trifluormetil- 5-metóxi-penta-2,4-dienonitrilas (Ar = Ph, 4-F-C6H4, 4-Br-C6H4, 4-Me-C6H4 e 4- MeO-C6H4) (5), em um sistema de refluxo utilizando água como solvente, na presença de HCl e 1 equivalente de ZnBr2, obtendo-se os produtos esperados com rendimentos entre 88 e 100%.As piridiniminas, piranonas e dienos obtidos neste trabalho foram identificados e caracterizados por Ressonância Magnética Nuclear de Hidrogênio (RMN H1), Ressonância Magnética Nuclear de Carbono-13 (RMN C13), Espectroscopia de Massas (CG-MS-EI), Espectroscopia de Massas de Alta Resolução (HRMS-ESI) e Análise Elementar.

Stilbene phytoalexins such as resveratrol, 1, and the arachidins, including arachidin-1,2, are naturally synthesised by peanut (Arachis hypogaea) plants. The peanut phytoalexins are polyphenolic compounds consisting of a stilbene backbone, with a number of derivatives also possessing a prenyl moiety. These distinctive phytoalexins have gained attention, as they exhibit various biological activities, for instance arachidin-1, 2, has been reported to be more potent than resveratrol, 1, in the inhibition of lipopolysaccharide-induced expression of cyclooxygenase-2 (COX-2) and COX-2 mRNA, in vitro at doses that were low in cytotoxicity. Additionally the various arachidins have recently been shown to exhibit their anti-inflammatory properties, through the inhibition of a number of inflammatory mediator pathways. In this work, various routes into the synthesis of arachidin-1, 2, are described, via use of the Horner-Wadsworth-Emmons (HWE) reaction. Three different methodologies were explored, the first approach involving silyl ether (TIPS or TBDMS) protected benzaldehydes, proved unsuccessful due to cleavage of the silyl ether protecting groups, in basic and/or acidic conditions. This led to an alternative approach, whereby formation of the stilbene backbone proceeded via the regioselective demethylation of an acetal in the presence of sodium metal, subsequent electrophilic substitution using iodomethane and finally acetal hydrolysis of the acetal, gave the isolated aldehyde in moderate yield (52 %). Coupling of the aldehyde with the substituted benzylphosphonate, via the HWE reaction gave the desired trans-stilbene in good yield (86 %), however incorporation of the prenyl side chain proved to be challenging via the Wohl-Ziegler bromination. Further adaptation of the aforementioned route, whereby alkylation using diethyl iodomethylphosphonate, enabled the incorporation of the prenyl moiety and the subsequent construction of the trans-stilbene backbone, gave the 4-(3-methyl-but-1- enyl)-3,5,3',4'-tetramethoxystilbene, 3, albeit in poor yield (47 %). The final step involving demethylation using BBr3 gave arachidin-1, 2, also in poor yield (30 %), nevertheless this approach has been proved to be a successful route for the total synthesis of arachidin-1, 2, however optimised studies are required in order to obtain the desired compound in quantitative yields. Synthetic analogues of resveratrol, 1, are also known for their biological activities, including anti-inflammatory and chemopreventative properties. Recently, the anti-proliferative activity of a number of stilbenesulfonamides, against the National Cancer Institute's 60 (NCI-60) human tumour cell line has been reported. Furthermore, the anti-inflammatory effects of novel heterocyclic methylsulfone and sulfonamide analogues, via inhibition of the COX-2 protein have also been published, however both synthetic routes described require a total of six or seven steps, from the sulfanilamide and are limited to the synthesis of primary sulphonamides (SO2NH2). In this work, an efficient three step synthesis has been designed and successfully implemented, proceeding via chlorosulfonation of diethyl benzylphosphonate, to form the sulfonyl chloride intermediate. Aminolysis of the sulfonyl chloride intermediate was then performed, using a range of primary, secondary and cyclic alkyl amines, as well as aromatic amines; including ammonia, dimethylamine, morpholine and diphenylamine. Finally, formation of the stilbene backbone with various substituted aldehydes, via the HWE reaction offered a short, versatile and alternative route to the synthesis of novel primary, secondary and tertiary trans-stilbene benzenesulfonamides and heterocyclic analogues, in yields of 42 - 100 %. The activity of a selection of the synthesised stilbene benzenesulfonamides was evaluated against the human lung adenocarcinoma epithelial cell line (A549). Amongst the compounds tested, analysis of the data showed that the novel analogue, 4, was found to be the most potent compound, with a GI50 of 0.1 μM. Comparison with the previously published data found analogue, 4, to be approximately 500-fold more potent than the lead compound resveratrol, 1, (GI50 = 51.64 μM) and approximately twice as potent than 5-fluorouracil (GI50 = 0.189μM), a chemotherapy drug used to treat various forms of cancer 8. Overall, these results demonstrate that the total synthesis of trans-arachidin-1, 2, can be achieved via a five step methodology. A versatile route to the synthesis of novel stilbene benzenesulfonamides has also been successfully achieved, amongst the compounds synthesised one appears to show promising anticancer activity, and warrants further investigation (i.e. in vitro studies using other cancer cell lines, and the synthesis of additional compounds using analogue, 4, as a lead compound).

In this work, we demonstrate the first synthesis of vinylene-linked 2D CPs, namely, 2D poly(phenylenequinoxalinevinylene)s 2D-PPQV1 and 2D-PPQV2, via the Horner–Wadsworth–Emmons (HWE) reaction of C2-symmetric 1,4-bis(diethylphosphonomethyl)benzene or 4,4′-bis(diethylphosphonomethyl)biphenyl with C3-symmetric 2,3,8,9,14,15-hexa(4-formylphenyl)diquinoxalino[2,3-a:2′,3′-c]phenazine as monomers. Density functional theory (DFT) simulations unveil the crucial role of the initial reversible C−C single bond formation for the synthesis of crystalline 2D CPs. Powder X-ray diffraction (PXRD) studies and nitrogen adsorption-desorption measurements demonstrate the formation of proclaimed crystalline, dual-pore structures with surface areas of up to 440 m2 g−1. More importantly, the optoelectronic properties of the obtained 2D-PPQV1 (Eg=2.2 eV) and 2D-PPQV2 (Eg=2.2 eV) are compared with those of cyano-vinylene-linked 2D-CN-PPQV1 (Eg=2.4 eV) produced by the Knoevenagel reaction and imine-linked 2D COF analog (2D-C=N-PPQV1, Eg=2.3 eV), unambiguously proving the superior conjugation of the vinylene-linked 2D CPs using the HWE reaction.

Made available in DSpace on 2015-05-14T13:00:07Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 4230620 bytes, checksum: 21a141e2826d984369bb98c91a40386b (MD5) Previous issue date: 2014-05-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The phenylpropanoid esters of monoterpene alcohols are usually found in low concentrations in natural environments, which usually prevents some studies of toxicity and tolerance. Isolation from natural sources generally do not provide adequate quantities, mainly due to their occurrence at low concentrations. Substances such as: Bornyl Benzoate, Bornyl Salicylate, Bornyl p-coumarate, Bornyl Ferulate, Bornyl 3,4-methylenedioxy-trans-Cinnamate and trans-caffeate of α-Terpineol have presented several interesting pharmacological activities. This work aims to present alternatives for the preparation of these esters pathways such reactions Dartzen for preparation of acyl chlorides, esterification reactions of the type Shotten-Baumann reaction and the use of Wittig-Horner in getting the benzene esters of cinnamic some monoterpene alcohols such as (-)-borneol and α-terpineol. The identification of synthesized compounds was performed by analysis of 1H and 13C NMR and the data were compared with those in the literature for unambiguous assignment. The Shotten-Baumann reactions used to obtain the esters derived from (-)-borneol showed appropriate, to give yields between 84 and 40%. For the preparation of trans-caffeate of α-terpineol a Wittig-Horner reaction, with a yield of 20%, requiring further studies. / Os ésteres fenilpropanóides de álcoois monoterpênicos normalmente são encontrados em baixas concentrações nos meios naturais, o que normalmente inviabiliza alguns estudos de toxicidade e tolerância. O isolamento a partir de fontes naturais geralmente não provê quantidades adequadas, principalmente devido sua ocorrência em baixas concentrações. Substâncias como: Benzoato de Bornila, Salicilato de Bornila, p-Cumarato de Bornila, Ferulato de Bornila, 3,4-metilenodioxi-trans-Cinamato de Bornila e o trans-Cafeato de α-Terpineol têm apresentado diversas atividades farmacológicas interessantes. Este trabalho tem como objetivo apresentar vias alternativas para a preparação destes ésteres, como reações de Dartzen para preparação de cloretos de acila, reações de esterificação do tipo Shotten-Baumann e o uso da reação de Wittig-Horner, na obtenção de ésteres benzênicos, cinâmicos de alguns álcoois monoterpênicos como o (-)-borneol e o α-terpineol. A identificação dos compostos sintetizados foi realizada através de análises de RMN 1H e 13C e os dados foram comparados com os da literatura para atribuição inequívoca. As reações de Shotten-Baumann empregadas na obtenção dos ésteres derivados do (-)-Borneol demonstraram adequadas, obtendo-se rendimentos entre 84 a 40%. Para a preparação do trans-Cafeato de α-Terpineol foi utilizada a reação de Wittig-Horner, com rendimento de 20%, necessitando de mais estudos.

The interest in two-dimensional conjugated polymers (2D CPs) has increased significantly in recent years. In particular, vinylene-linked 2D CPs with fully in-plane sp2-carbon-conjugated structures, high thermal and chemical stability, have become the focus of attention. Although the Horner-Wadsworth-Emmons (HWE) reaction has been recently demonstrated in synthesizing vinylene-linked 2D CPs, it remains largely unexplored due to the challenge in synthesis. In this work, we reveal the control of crystallinity of 2D CPs during the solvothermal synthesis of 2D-poly(phenylene-quinoxaline-vinylene)s (2D-PPQVs) and 2D-poly(phenylene-vinylene)s through the HWE polycondensation. The employment of fluorinated phosphonates and rigid aldehyde building blocks is demonstrated as crucial factors in enhancing the crystallinity of the obtained 2D CPs. Density functional theory (DFT) calculations reveal the critical role of the fluorinated phosphonate in enhancing the reversibility of the (semi)reversible C−C single bond formation.