Dissertations / Theses on the topic 'Benzoxazinones'

Palladium-catalysed carbonylative multicomponent reactions have proven useful for the synthesis of structurally diverse compounds. Carbon monoxide serves as an atom-efficient, one-carbon building block, which allows for further structural elaboration of the carbonyl compound. By varying the components of the carbonylative multicomponent reaction, considerable product diversity can readily be attained. However, due to the reluctance to use toxic CO gas, considerable efforts have been directed at exploring non-gaseous approaches. The work described in this thesis has mainly focused on the development of palladium(0)-catalysed, carbonylative multicomponent synthetic methodology, using the non-gaseous CO source molybdenum hexacarbonyl, in the synthesis of heterocycles and other biologically relevant functional groups. The first part of this work describes the development of a non-gaseous carbonylative Sonogashira cross-coupling of bifunctional ortho-iodoanilines and terminal alkynes. Where 4-quinolones were synthesised via a carbonylation/cyclisation sequence. Using a similar synthetic strategy, three different N-cyanobenzamide intermediates were prepared by palladium-catalysed carbonylative couplings of various aryl halides and bromides and cyanamide. The formed intermediates provided a basis for further chemical transformations. First, ortho-iodoanilines were carbonylatively coupled with cyanamide and subsequently cyclised to yield heterocyclic 2-aminoquinazolinones. Next, building on those findings, the same synthetic strategy was applied to ortho-halophenols to provide a highly convenient domino carbonylation/cyclisation method for the preparation of benzoxazinones. The developed method was used to evaluate the efficiency of various non-gaseous CO sources. Third, the palladium-catalysed carbonylative synthesis of N-cyanobenzamides, was used to produce biologically relevant N-acylguanidines with considerable product diversity. Finally, one of the developed carbonylative methodologies was used in the preparation of potential NDH-2 inhibitors based on a quinolinyl pyrimidine scaffold. The prepared compounds were biologically evaluated in terms of inhibition of oxidoreductase NDH-2 and antibacterial activity on Gram-negative bacteria, S. aureus and Mtb. The biological evaluation revealed that some of the quinolinyl pyrimidines exerted inhibitory activity on the NDH-2 enzyme and possessed antibacterial properties. The work described in this thesis has been devoted to the development of non-gaseous one-pot, multicomponent carbonylation/cyclisation and carbonylation/amination reactions. The described methods offer highly attractive synthetic strategies that can be of great value to synthetic and medicinal chemists.

Kyoto University (京都大学)
0048
新制・課程博士
博士(農学)
甲第10906号
農博第1412号
新制||農||891(附属図書館)
学位論文||H16||N3917(農学部図書室)
UT51-2004-G753
京都大学大学院農学研究科応用生命科学専攻
(主査)教授 西岡 孝明, 教授 遠藤 隆, 教授 佐藤 文彦
学位規則第4条第1項該当

The principal aims of this project are to develop an understanding of colour and constitution relationships and the factors which influence the fluorescence properties in benzoxazinone-based fluorescent dyes, aza analogues of coumarin dyes, to explore the synthesis of a range of these benzoxazinone-based fluorescent dyes and to investigate their UV/visible and fluorescent spectral properties. A particular focus of this investigation was optimized of the synthesis of the dyes and the effect of solvents and other environmental influences on the electronic absorption and emission spectra of the dyes which might be usefully explored to give biological probe molecules. Molecular modeling studies using the CAChe system (AMI, MM2 PM3, ZINDO calculations) and PPP-MO calculations were used to investigate relationships between the chemical structure, spectral properties and technical performance. Reasonable spectral correlations were found using PPP-MO calculations to predict the colour of the benzoxazinone dyes. Weak solid-state fluorescence was observed under UV-light for the benzoxazinone dyes. This interesting feature was investigated in two cases by x-ray crystallography to explore the reasons for this observation. A test for cytotoxicity was carried out on benzoxazinone and coumarin dyes by the ISO 10993-5 method, which showed slight toxicity for the dyes. On the basis of the results of the investigation it was concluded that the benzoxazinone dyes have potential as probe molecules for biological application. Textile dyeing procedures using the dyes as disperse dyes for polyester were optimized. Colour measurement and assessment of fastness properties were carried out on the dyed fabrics.

Nous nous sommes intéressés à l’interaction entre une Poacée, le maïs, et l’insecte Spodoptera frugiperda, afin d’étudier le principe de coévolution. Les Poacées synthétisent le DIMBOA, composé aux effets bactéricides, fongicides et insecticides. Les noctuelles comme S. Frugiperda, un ravageur du maïs, ont dû s’adapter à cette voie de biosynthèse. L’origine de la voie de biosynthèse du DIMBOA a été étudiée par une approche bioinformatique. Notre étude suggère que la voie de biosynthèse a été initiée par le réarrangement de deux gènes nouvellement dupliqués, Bx1 et Bx2, à l’extrémité d’un chromosome d’un Poaceae ancêtre. Bx2, un gène codant pour un P450, a ensuite été dupliqué pour mener aux 4 P450s de la voie qui ont ensuite évolué par des phénomènes de divergence fonctionnelle et/ou de sélection positive, menant à leur spécificité de substrat. Nous avons démontré par des approches métabolomiques et transcriptomiques que des maïs dont la voie de biosynthèse a été bloquée au niveau des gènes Bx1 et Bx3 pouvaient simuler des étapes évolutives ancestrales disparues. Nous avons alors comparé l’effet de l’ingestion du maïs normal et des mutants sur les larves de S. Frugiperda par des études toxicologiques et transcritomiques. Enfin, nous avons étudié l’impact toxicologique des différents intermédiaires de la voie sur larves d’insectes. Les résultats montrent qu’au cours de la coévolution, l’insecte S. Frugiperda a optimisé sa réponse à la voie de biosynthèse complète, mais n’est plus adapté aux étapes ancestrales de la voie et précurseurs du DIMBOA. Cette observation permet d’envisager la manipulation d’une défense constitutive du maïs contre un de ses principaux ravageurs
To study the principle of plant-insect co-evolution, we studied the interaction between a Poaceae, Zea mays, and the insect Spodoptera frugiperda. The Poaceae developed the DIMBOA-biosynthetic pathway, compound with bactericide, fungicide and insecticide effects. Noctuid moths like S. Frugiperda, a maize pest, had to coevolve when the pathway expanded. We studied the origin of the DIMBOA-biosynthetic pathway in Poaceae by a bioinformatic approach and demonstrated that the origin of the pathway was the rearrangement of two new duplicated genes, Bx1 and Bx2, at the tip of a chromosome of a poaceous ancestor. Bx2 was further duplicated, leading to the 4 P450s of the pathway which further evolved by functional divergence and/or positive selection processes, explaining their actual high substrate specificity. We also characterized maize lines for which the pathway was blocked in the Bx1 and Bx3 genes by metabolomic and transcriptomic approaches and demonstrated that they could be used to simulate disappeared evolutionary ancestral steps. We then compared the influence of the ingestion of wild type or Bx1 and Bx3 mutant plants on S. Frugiperda larvae by a toxicological study and a transcriptomic approach. Finally, we studied the toxicological impact of different pathway intermediates on insect larvae. Our results demonstrate that, during coevolution, the polyphagous insect S. Frugiperda has optimized its response to the entire pathway and is no longer adapted to ancestral steps of the pathway and DIMBOA precursors. This observation allows us to envisage the manipulation of a maize constitutive defense as a way to fight against one of its main pest

Orientador: Pedro Luis da Costa Aguiar Alves
Resumo: As cultivares de cana-de-açúcar plantadas atualmente são resultado de melhoramentos genéticos que foram realizados visando o incremento na produtividade, mas esta seleção resultou na redução do potencial competitivo da espécie, que pode estar associada aos compostos alelopáticos presentes e/ou liberados por cada cultivar. A família Poaceae está entre as famílias mais pesquisadas em relação aos compostos alelopáticos, dentre eles os ácidos hidroxâmicos. A alelopatia caracteriza-se pelo efeito de uma planta no crescimento e estabelecimento de outra, por meio da produção e liberação de compostos químicos secundários para o ambiente. Com isto, o objetivo foi avaliar a interferência entre plantas daninhas e cana-de-açúcar e caracterizar o potencial alelopático de cana-de-açúcar, cultivares CTC 2 e IAC 911099, pelo método de liberação por exsudação radicular; identificar ácidos hidroxâmicos liberados por exsudação radicular; isolar frações e substâncias ativas de cana-de-açúcar. Para avaliar a interferência entre cana-de-açúcar e plantas daninhas foi utilizado o método de plantas em convivência, em caixas com e sem interferência radicular, com as espécies Ipomoea hederifolia (corda-de-viola), Urochloa decumbens (capim-braquiária) e Amaranthus viridis (caruru-de-mancha). A avaliação de possível efeito fitotóxico de exsudato radicular ocorreu a partir da avaliação de germinação e desenvolvimento das espécies Lactuca sativa (alface), Solanum lycopersicum (tomate), I. hederifolia, U. d... (Resumo completo, clicar acesso eletrônico abaixo)
Abstract: - Sugarcane cultivars planted nowadays are a result of genetic enhancement that aimed for productivity improvement; however, this diminished the species' competitive potential, which could be associated with the allelochemicals present or released by each variety. The Poaceae family resides among the most studied families regarding allelochemicals, hydroxamic acids amid them. Allelopathy is characterized by the influence of one plant on the growth and establishment of another plant through the production and release of secondary metabolites to the environment. This way, the objective was to assess interference and characterize the allelopathic potential of sugarcane, CTC 2 and IAC 911099 cultivars, through the root exudation release method; identify hydroxamic acids released by root exudation; isolate fractions and active substances of sugarcane. The plant in coexistence method is used to evaluate the interference between sugarcane and weed, in boxes with and without root interference, with weed species Ipomoea hederifolia (morning glory), Urochloa decumbens (signal grass) e Amaranthus viridis (slender amaranth). The evaluation of possible phytotoxic effect of root exudate is assessed by the evaluation of germination and development of the species Lactuca sativa (lettuce), Solanum lycopersicum (tomato), I. hederifolia, U. decumbens and A. viridis planted in sand that previously contained seedlings of sugar cane. To identify the hydroxamic acids BOA, MBOA, DIBOA and DIMBOA the... (Complete abstract click electronic access below)
Doutor

Le développement de nouvelles méthodologies de synthèse toujours plus efficaces, sélectives et éco-compatibles apparaît comme un défi permanent tant l’intérêt suscité pour les composés hétérocycliques est important. Ce projet de thèse s’articule autour de plusieurs axes dans ce domaine.Tout d’abord, nous avons exploité la réactivité des N-(sulfonyl) et N-(sulfamoyl)aziridines en tant que précurseurs de dipôles 1,3 en vue de préparer divers 1-azaspiro[5.n]alcanes. L’étude mécanistique de cette réaction de cycloaddition [3+2] réalisée par calculs DFT permet de montrer que l’étape cinétiquement déterminante de la réaction est la formation du dipôle 1,3 ; la force motrice étant la fermeture du cycle à cinq chaînons.Nous nous sommes également attachés à valoriser le savoir-faire du laboratoire dans le domaine des transferts catalytiques de nitrènes (aziridination et amination C-H) dans le cadre du projet de synthèse totale de la pactamycine, aminocyclopentitol hautement fonctionnalisé.Par ailleurs, la mise au point d’une cascade Passerini-Smiles/Réduction/Cyclisation et d’une séquence monotope Passerini-Double-Smiles/SNAr permet un accès rapide et efficace à des motifs hétérocycliques de type 1,4-benzoxazin-3-ones. Conduisant à des familles régioisomères de produits, ces deux voies de synthèse se sont avérées complémentaires.Parallèlement, une nouvelle méthodologie basée sur l’ouverture pallado-catalysée de thiocyclopropanes a permis d’obtenir de nouveaux hétérocycles de type thiochromènes. Compte tenu des nombreuses fonctionnalisations envisageables, ces composés semblent très prometteurs dans le domaine de la chimie hétérocyclique.Enfin, des études électrochimiques et RMN couplées à des calculs DFT ont été entreprises afin d’élucider le mécanisme mis en jeu lors des couplages pallado-catalysés entre un halogénure d’aryle, un isonitrile et un nucléophile
The development of new and more efficient synthetic methodologies, selective and eco-friendly seems to be an ongoing challenge as the interest in the heterocyclic compounds is important. All the studies performed during the last three years are divided in several axes in this field.First, the reactivity of N-(sulfonyl) and N-(sulfamoyl) aziridines as precursors of 1,3-zwitterionic species was explorated in order to obtain various 1-azaspiro[5.n]alkanes. The mechanism of the reaction has been studied by DFT calculations. The initial formation of the zwitterionic 1,3-dipole has been found to be the rate-determining step whereas the five-membered ring closure appeared to be the driving force.We tried to apply our expertise in the field of catalytic nitrene transfers (aziridination and C-H amination) to the total synthesis of pactamycin, highly functionalized aminocyclopentitol compound.Furthermore, the developments of a Passerini-Smiles/reduction/cyclization cascade and of a one-pot Passerini-Double-Smiles/SNAr sequence provide straightforward and efficient accesses to 1,4-benzoxazin-3-ones. These paths are complementary as they lead to regioisomers.Meanwhile, a new methodology based on Pd-catalyzed thiocyclopropanes ring opening gave thiochromenes. Due to their high synthetic potential, these compounds appear to be very promising scaffolds in heterocyclic chemistry.Finally, electrochemical and NMR studies coupled with DFT calculations have been done in order to elucidate the mechanism involved in the Pd-catalyzed couplings between an aryl halide, an isocyanide and a nucleophile

Les plantes dans leur environnement établissent des interactions avec des micro-organismes du sol. Parmi ces interactions nous pouvons distinguer les symbioses associatives mettant en jeu des bactéries PGPR (Plant Growth Promoting Rhizobacteria). L’impact de ces microorganismes phytobénéfiques (Azospirillum, Pseudomonas…) sur le métabolisme de la plante hôte est encore mal connu. Le modèle d’étude que nous avons choisi dans le cadre de ce travail est Zea mays L. qui peut établir de nombreuses symbioses associatives avec des PGPR. Pour étudier les effets de ces micro-organismes sur le maïs, deux approches ont été développées faisant notamment appel à des outils de profilage métabolique pour i) déterminer l’impact de la simple inoculation micro-organismes sur le métabolisme secondaire racinaire et des parties aériennes de la plante hôte, et ii) évaluer les effets physiologiques de consortia microbiens comprenant Azsopirillum, Pseudomonas et Glomus. Les résultats de ce travail démontrent la place prépondérante des composés de type benzoxazinoide (benzoxazolinone et benzoxazinone) dans les interactions et la modulation de leur synthèse induite par les inocula. Par ailleurs nos travaux mettent également en évidence que la réponse métabolique de la plante à l’interaction avec les micro-organismes est dépendante de l’espèce et de la souche bactérienne considérée suggérant ainsi un phénomène de reconnaissance entre les deux organismes
In environment, plant performed some interactions with soil microorganisms. From these interactions, associative symbiosis involving PGPR bacteria (Plant Growth Promoting Rhizobacteria) can be considerate. Impact of phytobenefic microorganisms (Azospirillum, Pseudomonas…) leading to associatives interactions, on host plant metabolisms, still poorly understood. Zea mays L. was choose as study model because it can enter in various associatives symbiosis with Plant growth Promoting Rhizobacteria. To study effects of these microorganisms on maize, two approaches were developed thanks to metabolite profiling tools to (i) determine the impact of a single microorganism inoculation on host plant roots and shoots secondary metabolisms and (ii) evaluate physiological effect of microbial consortia including Azospirillum, Pseudomonas and Glomus species. Results of this work showed the major place of benzoxazinoids compounds (benzoxazolinone and benzoxazinone) in plant/microbe interaction and their synthesis modulation induced by inocula. Besides, our works brings to light that the metabolic answer of the plant to the interaction with microorganisms is dependent on species and bacterial strain suggesting a recognition phenomenon between both organisms

Pfropfcopolymere definierter Architektur wurden auf Basis von drei neu synthetisierten multifunktionellen Kopplungsreagenzien mit N-Acyllactam- und Benzoxazinongruppen über zweistufige selektive Schmelzereaktionen erfolgreich synthetisiert. Dabei wurde die Selektivität der Schmelzereaktionen durch die Reihenfolge der Zugabe der funktionellen Ausgangsoligomere und die Temperatur kontrolliert. Die erhaltenen Pfropfcopolymere stellen thermoplastische Elastomere mit hoher Zugfestigkeit und zugleich hoher Dehnung dar.

碩士
朝陽科技大學
應用化學系碩士班
97
Contents of the benzoxazinone derivatives in soils from growing genetically-modified plant and non genetically-modified plant were difference at genetically-modified papaya of Hawaii with an environmental security assess from United States Department of Agriculture (USDA). The study, determined of benzoxazinone derivatives in soil from growing genetically-modified plant by HPLC, suggest according to the USDA and consulted the method of European Union Project. Extraction conditions for benzoxazinone were MeOH (1% HOAc). The soil from Taitung peinan and Miaoli touwu was a loam and sandy clay loam. Extraction conditions for benzoxazinone extraction were ultrasonic. BOA is not detected in the soils which grew genetically-modified plants and non-genetically-modified plants. The quantity of MBOA contained in the soil which grew genetically-modified plants (0.61±0.05 μg/g soil) is higher than the quantity contained in the soil which grew non-genetically-modified plants (0.41±0.04 μg/g soil). The accuracy RSD of MBOA contained in the soil which sandy loam (7.4%) is best than accuracy RSD contained in the soil which clay loam (9.2%) and loam (10.9%). The recovery of BOA and MBOA by using MeOH (1.0% HOAc) from the loam are 97.2 and 116.0% individually, in which 12 μg standard solution was added. The recovery of BOA and MBOA by using MeOH (1.0% HOAc) from the sandy loam are 99.6 and 103.1% individually, in which 12 μg standard solution was added. For sandy loam, the recovery of BOA and MBOA are 99.6% and 103.1% individually. The MDL of BOA and MBOA in the loam are 0.12 μg/g soil. These MDL in sandy loam for BOA and MBOA are 0.10 and 0.08 μg/g soil individually.

碩士
國立中央大學
化學學系
103
PartI. According to many researches, abnormal expression of the sialyltransferase has been found to actually connect with many cancers. Therefore, purposes and objectives of this study are making effort to develop effective sialyltransferase inhibitors and regulate the level of sialyltransferase expression.In the thesis, the main structure of our compounds are lithocholic acid. We used high efficient and selective reagent─Selectfluor to add a fluorine atom at the C4 position as modification, and we synthesized fluorinated compound of Lith-O-Asp-NBD as effective anti-cancer compound further.Through MTT assay and Wound healing assay experiment to discuss fluorinated compound’s influence on biologically activity. Interestingly, We found that compounds JO-5b, JO-13a, JO-13b possess potent anti-metastasis ability. PartII. Fluorescent labeling has the advantage of high sensitivity and good selectivity for the use in a wide range of applications. In recent years, novel molecular imaging agents were developed for the use of clinical translation through early lesion detection, molecular targeted therapy, therapeutic monitoring, and the development of new anti-cancer drugs. This action significantly improves diagnosis and therapy in patients with breast cancer metastasis. In this thesis, the main structure of our compounds is benzoxazinone. We modified its functional group to explore the relationship between structure and fluorescent quantum yield of molecular probes. Through analysis of the optical property, we found that Jo-35 has the highest quantum yield (Φ = 0.39) compared to that of others. Intramolecular hydrogen bond was confirmed in the skeleton between oxygen atom and amino group of the benzene ring. Molecular probes drop the fluorescent property if the intramolecular hydrogen bond is absent due to replacement of the amino group by other atom and/or moiety.

Pfropfcopolymere definierter Architektur wurden auf Basis von drei neu synthetisierten multifunktionellen Kopplungsreagenzien mit N-Acyllactam- und Benzoxazinongruppen über zweistufige selektive Schmelzereaktionen erfolgreich synthetisiert. Dabei wurde die Selektivität der Schmelzereaktionen durch die Reihenfolge der Zugabe der funktionellen Ausgangsoligomere und die Temperatur kontrolliert. Die erhaltenen Pfropfcopolymere stellen thermoplastische Elastomere mit hoher Zugfestigkeit und zugleich hoher Dehnung dar.