Functionalization of hydrocarbons via a free-radical based allyl transfer reaction using various allyl bromide substrates has been previously studied. The work described in this dissertation focuses on the replacement of Br by phthalimido-N-oxyl (PINO ) which helps make this chemistry environmentally friendly. To replace Br with PINO , replacement of previously used allyl-bromide substrates with new allyl-PINO substrates were necessary. Various allyl- PINO compounds were synthesized and the use of these allyl-phthalimido-N-oxyl (allyl-PINO) compounds for the functionalization of various alkyl aromatic hydrocarbons is demonstrated. Kinetic studies were performed to observe the efficiency of the new chain reaction compared to the previously reported studies with allyl-bromides. We recently discovered that these allyl substrates are useful for the functionalization of ethers and acetals. The functionalization of various cyclic and acyclic ethers was performed using these allyl transfer reactions. This reaction was also performed in-solution, which allowed us to perform these reactions at low reagent concentrations. Kinetic chain lengths were measured for these reactions. High chain lengths were observed for all used ethers. Kinetic studies to investigate the rate of radical addition-elimination processes were performed using laser flash photolysis and competition kinetics. These experiments helped us to measure the reactivity and selectivity of PINO as a chain carrier in comparison with Br. Additionally, a new competition experiment was designed to study the relative rate constant for the 􀈕-fragmentation process. For this experiment a novel substrate that contains two leaving groups, Br and PINO, was synthesized, and the relative rates of elimination of Br vs PINO were compared. / Ph. D.

Die vorliegende Dissertation beschäftigt sich mit der Synthese und Charakterisierung von Übergangsmetallkomplexen und deren Anwendungen in der MOCVD (= metal-organic chemical vapor deposition), sowie als Precursoren zur Darstellung von Nanopartikeln und Nanokompositen. Ein Schwerpunkt dieser wissenschaftlichen Arbeit liegt dabei in der Entwicklung von Me-, tBu- und SiMe3-substituierten Manganhalbsandwichkomplexen für die Generierung dünner Mangan-basierter Schichten mittels MOCVD-Technik. Die gezielte strukturelle Veränderung des Cyclopentadienyl-Liganden beeinflusst die physikalischen und chemischen Eigenschaften dieser Verbindungen, welche systematisch untersucht werden. Ein weiteres zentrales Thema dieser Arbeit ist die Entwicklung von Bis(β-diketonato)- und Allyl-(β-diketonato)-palladium(II) Verbindungen als MOCVD-Precursoren. Hierbei dienen asymmetrische β-Diketonate des Typs CH3COCCO(CH2)n (n = 3, 4) als Liganden. Zudem wird durch Substitutionsreaktionen mit Me- und tBu-Gruppen am η3-Allyl-Liganden Einfluss auf die Stabilität der Verbindungen genommen. Die Abscheidung dieser Precursoren führt, in Abhängigkeit des verwendeten Reaktivgases, zur Bildung von Palladium- bzw. Palladiumoxid-Schichten. Zudem wird die Synthese und Charakterisierung von Co(II)-Carboxylaten des Typs [Co(CO2CRR´(OC2H4)nOMe)2] (n = 1, 2; R = H, R´ = Me; R = H, R´ = Ph) beschrieben. Stellvertretend wird eine Verbindung als Single-Source Precursor zur Darstellung von Co3O4-Nanopartikeln eingesetzt. Darüber hinaus wird die Inkorporation von Co3O4-Nanopartikel in organisch-anorganische Hybridmaterialien mittels Zwillingspolymerisation vorgestellt.

Die vorliegende Dissertation beschäftigt sich mit der Synthese und Charakterisierung von Übergangsmetallkomplexen und deren Anwendungen in der MOCVD (= metal-organic chemical vapor deposition), sowie als Precursoren zur Darstellung von Nanopartikeln und Nanokompositen. Ein Schwerpunkt dieser wissenschaftlichen Arbeit liegt dabei in der Entwicklung von Me-, tBu- und SiMe3-substituierten Manganhalbsandwichkomplexen für die Generierung dünner Mangan-basierter Schichten mittels MOCVD-Technik. Die gezielte strukturelle Veränderung des Cyclopentadienyl-Liganden beeinflusst die physikalischen und chemischen Eigenschaften dieser Verbindungen, welche systematisch untersucht werden. Ein weiteres zentrales Thema dieser Arbeit ist die Entwicklung von Bis(β-diketonato)- und Allyl-(β-diketonato)-palladium(II) Verbindungen als MOCVD-Precursoren. Hierbei dienen asymmetrische β-Diketonate des Typs CH3COCCO(CH2)n (n = 3, 4) als Liganden. Zudem wird durch Substitutionsreaktionen mit Me- und tBu-Gruppen am η3-Allyl-Liganden Einfluss auf die Stabilität der Verbindungen genommen. Die Abscheidung dieser Precursoren führt, in Abhängigkeit des verwendeten Reaktivgases, zur Bildung von Palladium- bzw. Palladiumoxid-Schichten. Zudem wird die Synthese und Charakterisierung von Co(II)-Carboxylaten des Typs [Co(CO2CRR´(OC2H4)nOMe)2] (n = 1, 2; R = H, R´ = Me; R = H, R´ = Ph) beschrieben. Stellvertretend wird eine Verbindung als Single-Source Precursor zur Darstellung von Co3O4-Nanopartikeln eingesetzt. Darüber hinaus wird die Inkorporation von Co3O4-Nanopartikel in organisch-anorganische Hybridmaterialien mittels Zwillingspolymerisation vorgestellt.

Les propietats insecticides d’una sèrie d’esters d’al•lil va ésser avaluada en diferents insectes mitjançant diferents modes d’aplicació. L’acció per aplicació tòpica va variar en funció de l’ester d’al•lil aplicat. El cinamat i el naftoat d’al•lil van ser els compostos més actius front a ous i larves neonates de C. pomonella, G. molesta i L. botrana, mentre que el salicilat d’al•lil no va produir mortalitat a la major dosi assajada (10 mg/mL). El cinamat d’al•lil va ser l’únic ester actiu per aplicació tòpica en adults de A. pisum, mentre que tots els esters d’al•lil testatsvan ser actius en adults de T. castaneum. Els esters d’al•lil assajats van produir una pèrdua de la viabilitat cel•lular en les línees cel•lulars d’insectes quan va èsser mesurda mitjançant dos metodologies diferents (MTT i Blau de tripà), degut a una disrupció de les membranes cel•lulars. El cinamat d’al•lil va ser el compost més actiu i les cèl•lules procedents de l’aparell digestiu de Choristoneura fumiferana (Lepidòpter) les més sensibles. L’acció insecticida per ingestió va ser confirmada en larves de S. littoralis i C. pomonella, i en nimfes de A. pisum, senyalant l’aparell digestiu com a principal punt d’acció dels esters d’al•lil. Els corresponents àcids i dicloropropilesters van mostrar una menor o igual acció insecticida que els corresponents esters d’al•lil, deguda també, a una acció en la membrana cel•lular. Les diferències en l’acció dels compostos seria deguda a diferències en les propietats lipofíliques dels compostos i la seva interacció amb les membranes cel•lulars. Pel que fa a l’efecte dels esters d’al•lil en la comunicació química dels insectes, aquesta va tenir lloc en T. castaneum però no en A. pisum, el que es podria utilitzar per a mantenir els productes enmagatzemats lliures de T. castaneum. Pel que fa a C. pomonella i a L. botrana, tots els esters d’al•lil assajats van produir una resposta en les antenes dels mascles de C. pomonella, però tan sols el cinamat d’al•lil la va provocar en les femelles de C. pomonella i en mascles i femelles de L. botrana. Aquesta acció no es va veure reflexada en un increment de l’atracció de mascles cap a fonts amb l’ester d’al•lil i feromona en assajos en túnel de vent, però si en l’atracció de femelles. Aquest fet podria utilitzar-se per a incrementar el nombre de captures de femelles en trampes de feromona. Aquests resultats suggereixen un paper dels esters d’al•lil en el control de plagues, especialment del cinamat d’al•lil. / La acción insecticida de varios esteres de alilo fue testada en diversos insectos y mediante distintos modos de aplicación. La actividad por aplicación tópica varió en función del éster de alilo. El cinamato de alilo y el naftoato de alilo fueros los compuestos más activos en huevos y larvas neonatas de C. pomonella, G. molesta y L. botrana, mientras que el salicilato de alilo no produjo mortalidad a la dosis más alta testada (10 mg/mL). El cinamato de alilo fue el único éster activo por aplicación tópica en A. pisum mientras que todos los esteres testados lo fueron para T. castaneum. Los esteres de alilo estudiados produjeron pérdida de viabilidad celular en todas las líneas celulares de insectos cuando dicha viabilidad fue analizada mediante dos metodologías distintas (MTT y Azul de Tripano), y siendo ésta debida a la disrupción de la membrana celular. El cinamato de alilo fue el producto más activo, y las células del aparato digestivo de Choristoneura fumiferana (Lepidoptera) las más sensibles. La acción insecticida por ingestión en larvas de S. littoralis y C. pomonella, y en ninfas de A. pisum, fue confirmada y el aparato digestivo fue señalado como principal punto de acción de los esteres de alilo. Los correspondientes ácidos y dicloropropilesteres presentaron una menor o igual acción insecticida que los esteres de alilo siendo dicha acción también debida a un efecto en la membrana celular. Las diferencias en la acción de los distintos compuestos podrían ser debidas a diferencias en las propiedades lipofílicas de los compuestos y su interacción con las membranas celulares. Los esteres de alilo produjeron un efecto en la comunicación química de T. castaneum pero no en A. pisum, lo que podría utilizarse para mantener los productos almacenados libres de T. castaneum. En cuanto a C. pomonella y L. botrana, todos los esteres de alilo probados produjeron una respuesta en las antenas de los machos de C. pomonella, mientras que tan solo el cinamato de alilo la produjo en las antenas de hembras de C. pomonella y en machos y hembras de L. botrana. Esta respuesta no se tradujo en un aumento de la atracción de machos hacia cebos con mezclas de ester de alilo y feromona en ensayos de túnel de viento, pero si aumentó el número de hembras atraídas. Este hecho podría utilizarse par incrementar el número de hembras capturadas en trampas de feromona. Estos resultados, sugieren el papel de los esteres de alilo en el control de plagas, especialmente del cinamato de alilo.

Allyl methacrylate, AMA was polymerized by chemical initiator and by &amp / #947 / -radiation under different conditions. The polymer obtained is mostly gel type with some soluble fractions at lower conversions. Arrhenius activation energy is 82.3 kJ/mol for chemical initiated polymerization. The polymer was characterized by FT-IR, NMR, DSC, TGA, XPS, XRD, DLS, and MS methods. It was found that about 98-99% of allyl side groups retained as pendant even after completion of the polymerization, while 1-2% may give crosslinking and/or cyclization that yields lactones and anhydrides. The spectroscopic and thermal results of the work showed that the reaction is not cyclopolymerization, but may have end group cyclization. Molecular weight of 1.1x106 was measured by DLS. Therefore, insolubility is due to the high molecular weight of polymer, even in the early stage of polymerization rather than crosslinking. The Tg of PAMA was observed as 94&ordm / C before curing, upon curing at 150-200&ordm / C, Tg increased to 211&ordm / C as measured by DSC. The thermal treatment of polymer at about 350&ordm / C gave anhydride by linkage type degradation, following side group cyclization. The XPS analysis showed the presence of radical fragments of AIBN and CCl4 associated with oligomers. The MS and TGA thermograms showed two or three stage degradations depending on solubility. The first stage was mostly linkage type degradation for the fragmentation of pendant allyl groups at 225-350&ordm / C. In the second stage, at 395-515&ordm / C, the degradation is random scission and depolymerization.

Les revêtements poudres UV suscitent un développement croissant en raison, entre autres, de leurs qualités et de leur respect de la législation sur la minimisation des émissions polluantes. Un nouveau revêtement poudre UV à base de (co)polyamide de faible masse molaire et porteur de fonctions réactives sous UV a été élaboré en vue d'une application sur des supports sensibles aux hautes températures. Nous avons donc synthétisé un copolyamide 6/11/12 alpha, oméga-insaturé présentant une température de fusion de 107°C et une masse molaire moyenne en nombre de 7250 g/mol. L'irradiation sous UV de ce copolyamide, en présence de 4 % en masse de benzophénone, a permis, par polymérisation des doubles liaisons allyliques et formation des liaisons covalentes au niveau des ponts amide, de compenser la perte de cristallinité en le réticulant. Le revêtement obtenu, bien que restant à optimiser, a montré globalement de meilleures propriétés que celles des matériaux références fournis par Arkema.

In this project the factors influencing the stability and antimicrobial activity of allyl isothiocyanate (AITC) against Campylobacter jejuni, Salmonella or Listeria monocytogenes as well as factors that enhance sinigrin (glucosinolate in Oriental mustard) hydrolysis by these pathogens were investigated. The minimum inhibitory concentration (MIC) of AITC against 5 strains of each of Salmonella or L. monocytogenes, ranged from 60-100 ppm at 37 ºC. This was reduced to 10-40 ppm at 21 ºC and a further reduction to 5-10 ppm against strains of L. monocytogenes was observed at 4 ºC. This was attributed to greater stability of AITC as temperature was decreased. C. jejuni strains were more susceptible to AITC with MICs of 0.63-1.25 ppm and 2.5-5 ppm at 37 and 42 ºC, respectively. AITC was more inhibitory at ≤ 21 ºC against Salmonella with acidic pH or against L. monocytogenes with neutral pH. C. jejuni, Salmonella and L. monocytogenes strains and mixtures had the ability to degrade sinigrin to form inhibitory concentrations of AITC, and sinigrin hydrolysis was significantly enhanced by higher incubation temperature (21 ºC > 10 ºC > 4 ºC), the presence of 10 mM ferric or ferrous irons, and the presence of < 0.25% glucose. This project also investigated the antimicrobial activity of AITC or Oriental mustard extract alone or combined with ethylenediamine tetraacetic acid (EDTA), malic acid and acetic acid in edible antimicrobial coatings against C. jejuni and Salmonella on fresh, refrigerated, vacuum-packed chicken breasts or L. monocytogenes on refrigerated, cured roast chicken. Malic acid improved the antimicrobial activity of Oriental mustard extract against L. monocytogenes, while EDTA improved its activity against Salmonella. Incorporation of 25 to 50 µl/g AITC or 100 to 250 mg/g Oriental mustard extract in 0.5%κ-carrageenan/2%chitosan coatings, prepared using 1.5% malic or acetic acid, reduced L. monocytogenes on cooked, cured, vacuum-packed chicken slices 4.2 to > 7.0 log10 CFU/g, compared to uncoated chicken by 70 d at 4 ºC. In addition, 0.2%κ-carrageenan/2%chitosan coatings (prepared using a 1% acetic acid solution) containing 250 mg/g mustard extract or 50 µl/g AITC reduced Salmonella numbers on vacuum-packed chicken breasts 3.0 log10 CFU/g by 21 d at 4 ºC. Further, 0.2%κ-carrageenan/2%chitosan coatings containing 50 or 100 µl/g AITC reduced numbers of C. jejuni on fresh, vacuum-packed chicken breasts > 5.0 log10 CFU/g (C. jejuni cells were not detected) after 5 d storage at 4 ºC, while coatings containing 200 to 300 mg/g Oriental mustard extract or 25 µl/g AITC reduced C. jejuni numbers by 3.6 to 4.6 log10 CFU/g. Numbers of lactic acid and aerobic bacteria on poultry meat products were significantly reduced by the coatings. It is clear that κ-carrageenan/chitosan coatings containing either AITC, mustard extract alone or combined with EDTA, malic or acetic acid significantly reduced C. jejuni and Salmonella on fresh, refrigerated, vacuum-packed chicken breasts and L. monocytogenes on refrigerated, cured roast chicken, and consequently enhanced their safety.

The syntheses and characterization of the palladium complexes [Pd(accp)2] (7), [Pd(acch)2] (8), [Pd(η3-CH2CMeCH2)(accp)] (11), [Pd(η3-CH2CMeCH2)(acch)] (12), [Pd(η3-CH2CtBuCH2)(accp)] (13) and [Pd(η3-CH2CtBuCH2)(acch)] (14) (accp = 2-acetylcyclopentanoate; acch = 2-acetylcyclohexanoate) are reported. These complexes are available by the reaction of Haccp (2-acetylcyclopentanone) and Hacch (2-acetylcyclohexanone) with Na2[Pd2Cl6] forming 7 and 8 or with [(Pd(η3-CH2CRCH2)(μ-Cl))2] (9, R = Me; 10, R = tBu) forming 11–14. The molecular structures of 7, 8 and 14 are discussed. Complexes 7 and 8 consist of a square-planar coordinated Pd atom with two trans-positioned bidentate β-diketonate ligands. The asymmetric unit of 14 exhibits one molecule of the palladium complex and a half molecule of water. The thermal behavior of 7, 8 and 11–14 and their vapor pressure data were investigated to show, if the appropriate complexes are suited as CVD precursors for palladium layer formation. Thermogravimetric studies showed the evaporation of the complexes at atmospheric pressure upon heating. The vapor pressure of 7, 8 and 11–14 was measured by using thermogravimetric analysis, giving vapor pressure values ranging from 0.62 to 2.22 mbar at 80 °C. Chemical vapor deposition studies were carried out applying a vertical cold wall CVD reactor. Either oxygen or forming gas (N2/H2, ratio 90/10, v/v) was used as reactive gas. Substrate temperatures of 350 and 380 °C were utilized. With 11–14 dense and conformal as well as particulate palladium films were obtained, as directed by SEM studies, whereas 7 and 8 failed to give thin films, which is probably attributed to their high thermal stability in the gas phase. For all deposited layers, XPS measurements confirmed the partial oxidation of palladium to palladium(II) oxide at 380 °C, when oxygen was used as reactive gas. In contrast, thin layers of solely metallic palladium were obtained utilizing forming gas during the deposition experiments. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

A new free radical chain process for the allylation of hydrocarbons and some other substrates utilizing substituted allyl bromides (R-H + C=C-C-Br -> R-C-C=C + HBr) has been developed. Good to excellent yields were observed in all cases. Kinetic chain measurements and competition experiments were performed in order to elucidate the mechanism of the reaction. Overall, the results are consistent with a free radical chain process with bromine atom as the chain carrier. Substitution effects on the reactivity of the allyl bromides (CH2=C(Z)CH2Br) and their influence on the overall reaction rate were studied by conducting several competition experiments. The relative rate constants for addition of benzyl radical to CH2=C(Z)CH2Br are: Z=CN(180), COOEt(110), Ph(65), H(1.0). The trend of electronegativity/reactivity of these reactions was very similar to that reported for addition of benzyl radical to substituted alkenes. Other than alkyl aromatics (PhCH3, PhCH(CH3)2), other substrates (i.e., 2- propanol, phenyl cyclopropane) were also tested for this allylation reaction. The magnitude and scope of these reactions, and their synthetic utility is discussed. / Ph. D.

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