Synthesis of 4-substituted-3(2H)-furanones with novel luminescence properties

The objective of this project was to prepare a range of 4-substituted 3-(2H)-furanones, and to investigate the relationship between their molecular structures and photoluminescence properties. The effects of substituents and conjugated linker unit were also investigated. After generation of the key 3(2H)-furanone heterocycle, extension of the conjugated framework at the C-4 position was achieved through Pd(0)-catalysed coupling reactions. Chapter one of the thesis comprises a review of the relavent literature and is split into three sections. These include information about the prevalence of 3-(2H)-furanones as natural products and synthetic routes to 3-(2H)-furanones in general. The synthetic routes are divided according to the synthetic precursor employed. The final section of chapter one outlines the fundamental principles and application of photoluminescence to organic compounds in general. Chapter two contains the results of the research achieved in the course of this work and a discussion of the findings. Two routes were successfully employed to generate 4-unsubstituted 3-(2H)-furanone moieties: (i) base induced cyclisation of hydroxyenones and (ii) isoxazole chemistry. A number of methods which proved ineffective in the production of furanones with the desired substitution pattern are also detailed. The majority of this study was focused on the introduction of substituents at the C-4 position of the 3-(2H)-furanone ring. This was achieved through the use of Sonogashira and Suzuki cross coupling protocols for Pd(0) catalysed C-C bond formation. The further functionalisation of some compounds was performed using transfer hydrogenation and ���click chemistry��� methodologies. Finally, the photophysical properties of 3-(2H)-furanones prepared in this project are discussed and the effect of substitution patterns in a complementary ���push push��� and ���push pull��� manner have also been investigated. All the experimental data and details of the synthetic methods employed, for the compounds prepared during the course of this research is contained in chapter three together with the spectroscopic and analytical properties of the compounds prepared.

An investigation into reactivity and selectivity in cycloadditions of 1,3-dipoles with formamidines

The objective of this research was to investigate the synthesis of nitrile oxides and to study their reactivity in 1,3-dipolar cycloadditions with formamidines. Chapter one looks at the literature surrounding the 1,3-dipolar cycloaddition reaction. It explores the generation of 1,3-dipoles (mainly nitrile oxides) and dipolarophiles (predominantly amidines). It discusses the potential synthetic uses of the 1,3-dipolar cycloadducts. It examines both and inter- and intra-molecular cycloaddition reactions. It recognises the use of the 1,3-dipolar cycloadditions as a successful method in building natural products and oxadiazolines. The decomposition of oxadiazolines as a route to nitriles is also outlined in this chapter. Chapter two discusses the results of this research candidate. The preparation of nitrile oxide precursors - hydroximoyl halides - is outlined at first. The generation of nitrile oxides is then demonstrated, followed by the preparation of furoxans. Methods for preparing the reference materials (nitriles and ureas), which result from decomposition of oxadiazolines, then follow. The preparation of series of ��2-1,2,4- oxadiazolines via the 1,3-dipolar cycloaddition reaction is illustrated in this chapter. The selectivity of the addition of nitrile oxides to dipolarophiles was tested by competition reactions, which are also described in this chapter. NMR techniques were used in the study of the kinetics of the 1,3-dipolar cycloadditions used for the preparation of a series of ��2-1,2,4-oxadiazolines, which is addressed in this chapter. Chapter three charts the experimental procedures followed to gain results which are discussed in chapter two. It also outlines all analytical data produced during the course of this research.

Chemistry and synthesis of 3(2H)-furanones and 4,5-dihydro analogues: mechanistic investigations and stereochemical control

The subject matter of this thesis relates to the chemistry of the five-membered oxygen heterocycles ��� 3(2H)-furanones and their 4, 5-dihydro analogues. Chapter one of the thesis is a review of the relevant chemistry of the compounds: their synthesis and key transformations. In chapter two, new research on 3(2H)-furanones is outlined in two parts. The first describes an investigation into the cyclisation of ��'-trialkylsilyloxyenone adducts with arenesulfenyl and selenenyl chlorides into the corresponding sulfur and selenium substituted 3(2H)-furanones without the involvement of a Lewis acid catalyst. The study, largely involving in situ NMR techniques, identified key features associated with the formation and reaction of the chlorosulfide and chloroselenide intermediates, including operation of the Thorpe-Ingold effect. The knowledge gained in this study was applied (the second part) to the synthesis of vinyl substituted furanone systems from ��'-trialkylsilyloxydienones where choice of the reaction conditions and electrophilic reagent was a key feature. An important difference in the behaviour of arenesulfenyl and selenenyl halides towards conjugated dienes emerged from this work. This phase of the research concluded with a new synthesis of geiparvarin, a natural product possessing anti-tumour properties.

Nachrichtendienstpsychologie 3

Der Versuch, nachrichtendienstliche Fragestellungen unter psychologischen Aspekten zu betrachten, ist auf ein positives Interesse gesto��en. In den beiden B��nden Nachrichtendienstpsychologie 1 (Litzcke, 2003) und 2 (Schwan, 2004) der FH Bund erschienen eine Reihe von Aufs��tzen, die ein breites Themenspektrum behandeln. Mit Band 1 wurde eine Struktur eingef��hrt, die sich bew��hrt hat, und die daher auch f��r Band 3 beibehalten wird. Die Beitr��ge des Bandes 3 lassen sich wie folgt zuordnen: 1) Anwendungen vorhandener Konzepte der Psychologie und aus Nachbardisziplinen in den Nachrichtendiensten. Siehe hierzu die Beitr��ge von Scherer zur Moderation von Qualit��tszirkeln im Bundesnachrichtendienst, von Damm und Litzcke zur Akzeptanz des Sicherheitsakteurs ���Europa���, von Schwan zur Bedeutung aggressiven Verhaltens f��r die Arbeit der Nachrichtendienste, von L��hr zum kognitiven Interview und von Wiesen zu den M��glichkeiten einer Gespr��chssteuerung. 2) ��bertragung psychologischer Methoden auf das Forschungsgebiet Nachrichtendienste zur Gewinnung neuer Ergebnisse / Konzepte. Siehe hierzu die Beitr��ge von M��ller-Enbergs zu den Motiven f��r eine geheimdienstliche oder nachrichtendienstliche Kooperation bei den inoffiziellen Mitarbeitern der DDR-Staatssicherheit, von Horn zu den Einsatzm��glichkeiten der Operativen Fallanalyse und von Schmalzl zum Konstrukt Einsatzkompetenz. 3) Generierung eigenst��ndiger psychologischer Erkenntnisse und Methoden im Bereich Nachrichtendienste. Dieser Rubrik ist kein Beitrag des Bandes 3 zuzuordnen. Der Abschlussbeitrag von Freitag zur Anwendbarkeit von T��uschungsprinzipien der Zauberkunst in der nachrichtendienstlichen Arbeit entzieht sich dieser Struktur. Der Beitrag ist mit Augenzwinkern geschrieben und soll auch so gelesen werden. Die Themen der Aufs��tze sind nicht auf rein nachrichtendienstliche Aufgabenstellungen beschr��nkt. So werden beispielsweise auch Querschnittsproblematiken behandelt, die nicht nur einem Arbeitsbereich innerhalb der Nachrichtendienste zuzuordnen w��ren. Damit werden auch Themen behandelt, die ebenso in anderen Beh��rden und Institutionen von praktischer Relevanz sein k��nnen. So ist beispielsweise die Einrichtung von Qualit��tszirkeln kein spezifisches Thema der Nachrichtendienste. Da sich aber auch Nachrichtendienste mit der Qualit��tssteigerung ihrer Arbeit befassen, ist es angezeigt, entsprechende Ausarbeitungen in die Reihe Nachrichtendienstpsychologie zu integrieren. Auch in Band 3 werden interdisziplin��re Ans��tze und Verkn��pfungen mit der Polizeipsychologie vorgestellt, auch wenn die dort entwickelten Erkenntnisse und Methoden nicht ungepr��ft auf nachrichtendienstliche Aufgabenstellungen ��bertragen werden k��nnen. Gleichwohl k��nnen sich aus dem Kontakt zur Polizeipsychologie Anregungen f��r die Nachrichtendienstpsychologie ergeben.

Epistemologia feminista: profunditzant sobre el coneixement situat (part 3 de 4)

Ponent: Maria Puig de la Bellacasa / Presenta: V��ctor Jorquera

Recerca feminista en geograf��a: m��todes i pr��ctiques per a la visibilitzaci�� de la difer��ncia (part 3 de 4)

Ponent: Anna Ortiz / Presenta: B��rbara Biglia

Qu�� ens oculta el vel estad��stic? Reflexi�� feminista entorn del disseny i l'explotaci�� de les fonts de dades socials (part 3 de 5)

Ponent: Marta Luxan / Presenta: Ruth Vil��

Activitat 3. El paisatge

Material did��ctic del grup d'investigaci�� Observatori sobre la Did��ctica de les Arts (ODAS)

Departament de Did��ctiques Espec��fiques [n��m. 3]

��ltimes novetats en publicacions i treballs de recerca del Departament de Did��ctiques espec��fiques

N��mero 3 (1999)

N��mero 3 del Q��ern, un butllet�� bibliogr��fic de literatura i llengua catalanes antigues

Guia per a l'adaptaci�� a l'espai europeu d'educaci�� superior: 3. El vostre paper, estudiants = Gu��a para la adaptaci��n al espacio europeo de educaci��n superior: 3. Vuestro papel, estudiantes = Guide to adaptation to the European Higher Education Area: 3. Your role as a student

Aquest quadern forma part de la Guia per a l'adaptaci�� a l'espai europeu d'educaci�� superior

La reflexi??n metaling????stica de los alumnos de 4?? de ESO, 2?? de Bachillerato y 3?? de Grado en Estudios Hisp??nicos que implica la alteraci??n del orden oracional

Resumen basado en el de la publicaci??n. Resumen en ingl??s. Monogr??fico con el t??tulo: 'La reflexi??n metaling????stica y la ense??anza de la gram??tica'

An??lisis del aprendizaje de geometr??a espacial en un entorno de geometr??a din??mica 3-dimensional

Resumen tomado de la publicaci??n

E@ : Educaci??n Art??stica 3.0

Resumen basado en el de la publicaci??n

Necessitats pedag??giques de les fam??lies d???infants de 3 a 6 anys : un estudi de cas

Resumen basado en el de la publicaci??n