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The polarographic reduction of benzil derivativesMyers, Jon F. 01 January 1965 (has links)
The present study was undertaken to elucidate the electrochemical reduction
mechanisms of benzil derivatives using the techniques of polarography and controlled
potential electrolysis. Another objective of this study was to determine a
quantitative relationship between reactivity and structure. The electrochemical
experiments have been conducted in a 50% ethanol-water solvent over the pH range of 1.5 to 13.5. Potentiometric titrations and ultraviolet spectra were
obtained to help understand the ionization of hydroxy-substituted benzil derivatives
and how the ionization affects the polarographic reductions. Benzoin and
two benzoin derivatives were studied to help determine the reduction products.
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Chiral Separations By Enzyme Enhanced Ultrafiltration: Fractionation Of Racemic BenzoinOlceroglu, Ayse Hande 01 August 2006 (has links) (PDF)
In this study, a methodology for separation of chiral molecules, by using enhanced ultrafiltration system was developed. Benzoin was the model chiral molecule studied.
In the scope of developing this methodology, some parameters were investigated in the preliminary ultrafiltration experiments in order to set the operation conditions for enhanced ultrafiltration experiments. Due to the slight solubility of benzoin in pure water, 15% (v/v) Polyethylene glycol (PEG 400) and 30 % (v/v) Dimethyl sulfoxide (DMSO) were selected as cosolvents. Because of the high retention capacity of RC-10000 Da membranes for benzoin, a membrane saturation strategy was developed.
In polymer enhanced ultrafiltration (PEUF) experiments bovine serum albumin (BSA) was used as ligand. Effects of ligand concentration and pH on total benzoin retention and on enantiomeric excess (ee %) were investigated. Benzoin concentration was almost kept constant at ~10 ppm and ~50 ppm for 15% (v/v) PEG 400 and 30 % (v/v) DMSO cosolvents, respectively. It was observed that the increase either in pH or in BSA concentration yielded an increase in total benzoin retention. In 15% (v/v) PEG 400-water, with BSA concentration of 10000 ppm, at pH 10, total benzoin retention reached to 48.7%. For this cosolvent, at different pH values and at different BSA concentrations, all ee % values were about or less than 10%. When 50000 ppm BSA was dissolved in 30 % (v/v) DMSO-water, total benzoin retention increased to 41.3% at pH 10 and ee % reached 16.7 % at pH 11.
In enzyme enhanced ultrafiltration (EEUF) experiments, specific to benzoin, apo form of Benzaldehyde Lyase (BAL, E.C. 4.1.2.38) was used as ligand. These experiments were performed with constant ~ 10 ppm benzoin concentration in only 15% (v/v) PEG 400 &ndash / water solvent. Effect of BAL concentration on total benzoin retention and ee% was investigated. It was found that / for all the studied BAL concentrations in the range of 650- 1936 ppm total benzoin retention and ee % were kept almost constant at ~75% and ~60%, respectively.
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Benzaldehyde Lyase From Pseudomonas Fluorescens Biovar I Mediated Biotransformation For The Synthesis Of Chiral Alpha Hydroxy KetonesHosrik, Birsu Semra 01 January 2010 (has links) (PDF)
Optically active & / #945 / -hydroxy ketones are important subunits of many biologically active compounds and indispensable synthons for asymmetric synthesis. Benzaldehyde Lyase from Pseudomonas fluorescens Biovar I is a novel ThDP-dependent enzyme that catalyzes the synthesis of benzoin type chiral & / #945 / -hydroxy ketones starting from both benzaldehyde and racemic benzoin derivatives. Benzaldehyde Lyase is the first example of enzymes in the literature which leads to a chemical resolution of enantiomers of benzoin derivatives through a C-C bond cleavage reaction.
Chiral 2-hydroxypropiophenone derivatives are formed by benzaldehyde lyase (BAL), catalyzing C-C bond formation after a selective C-C bond cleavage of a benzoin derivative accepted as a substrate. The enzyme uses only the (R)-benzoin derivatives as substrate for the formation of (R)-HPP derivatives and it is highly stereoselective. Thus, in the presence of the acetaldehyde as the acceptor aldehyde, the C-C bond cleavage of the benzoin molecule followed by the carboligation of the acetaldehyde to yield chiral 2-hydroxy propiophenone derivatives.
Given the racemic benzoin to the enzyme as the substrate in the presence of acetaldehyde, both the racemic resolution of the substrate, revealing the unreacted (S)-Benzoin and the formation of the corresponding R-HPP occur.
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Cyanide-catalyzed C-C bond formation: synthesis of novel compounds, materials and ligands for homogeneous catalysisReich, Blair Jesse Ellyn 25 April 2007 (has links)
Cyanide-catalyzed aldimine coupling was employed to synthesize compounds
with 1,2-ene-diamine and ñ-imine-amine structural motifs: 1,2,N,N'-
tetraphenyletheylene-1,2-diamine (13) and (+/-)-2,3-di-(2-hydroxyphenyl)-1,2-
dihydroquinoxaline (17), respectively. Single crystal X-ray diffraction provided solidstate
structures and density functional theory calculations were used to probe isomeric
preferences within this and the related hydroxy-ketone/ene-diol system. The enediamine
and imine-amine core structures were calculated to be essentially identical in
energy. However, additional effects-such as ÃÂ conjugation-in 13 render an enediamine
structure that is slightly more stable than the imine-amine tautomer (14). In
contrast, the intramolecular hydrogen bonding present in 17 significantly favors the
imine-amine isomer over the ene-diamine tautomer (18).
Aldimine coupling (AIC) is the nitrogen analogue of the benzoin condensation
and has been applied to dialdimines, providing the first examples of cyclizations effected
by cyanide-catalyzed AIC. Sodium cyanide promoted the facile, intramolecular
cyclization of several dialdimines in N,N-dimethylformamide, methanol, or
dichloromethane/water (phase-transfer conditions) yielding a variety of six-membered
heterocycles. Under aerobic conditions, an oxidative cyclization occurs to provide the
diimine heterocycle.
Cyanide-catalyzed aldimine coupling was employed as a new synthetic method
for oligomerization. Nine rigidly spaced dialdimines were oxidatively coupled under
aerobic conditions to yield conjugated oligoketimines and polyketimines with
unprecedented structure and molecular weight (DP = 2 - 23, ~700 -8200 g/mol). The ñ- diimine linkage was established based on IR spectroscopy, NMR spectroscopy, size
exclusion chromatography, and X-ray crystallographic characterization of the model
oxidized dimer of N-benzylidene-(p-phenoxy)-aniline. Cyclic voltammetry indicates ptype
electrical conductivity, suggesting they are promising candidates for plastic
electronic devices.
The cyanide-catalyzed benzoin condensation reaction of 4-substituted
benzaldehydes followed by oxidation to the diketone, and the Schiff Base condensation
of two equivalents of o-aminophenol provides 2,3-(4-X-phenyl)2-1,4-(2-
hydroxyphenyl)2-1,4-diazabutadiene. The ligand is given the moniker X-dabphol.
These ligands are readily metallated to form M-X-dabphol complexes. The copper
complexes catalytically fix CO2 with propylene oxide to yield propylene carbonate. DFT
studies along with a comparison with Hammet parameters help validate and elaborate on
the catalytic cycle and the catalytic results obtained. The nickel complex is competent
for olefin epoxidation. Synthesis, characterization, X-ray structure, DFT analysis, and
catalytic activity of the parent nickel dabphol complex are reported.
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Development Of Acyl Anion Precursors And Their ApplicationsReis, Omer 01 March 2005 (has links) (PDF)
This thesis presents the development of new acyl anion precursors and their applications. The main concern of this thesis was to make use of acyl anion precursors in catalytic bond forming reactions. Toward this aim, previously known cyanide ion catalyzed cleavage of benzils was investigated in scope and efficiency in unsymmetrical benzoin condensation. Although benzils were proved to be useful entities as acyl anion precursors in benzoin condensation, they suffer some major drawbacks. Therefore acylphosphonates were proposed and investigated as a new generation of acyl anion precursor. They were found to be highly versatile and efficient in both catalytic unsymmetrical benzoin synthesis and other useful transformations.
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Enzymatic C-C bond formation using thiamine diphosphate dependent enzymes in a solid gas bioreactor /Mikolajek, Renaud. January 2008 (has links)
Zugl.: Aachen, Techn. Hochsch., Diss., 2008.
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Bicyclische Triazoliumsalze als Präkatalysatoren in der asymmetrischen Benzoin- und Acyloinkondensation und asymmetrische Synthese von Oxazolidin-2-onenKallfaß, Ulrike Silvia Gottfriede. Unknown Date (has links) (PDF)
Techn. Hochsch., Diss., 2002--Aachen.
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Total Synthesis of Natural Product Pterocarpans Useful as Selective Estrogen Receptor ModulatorsMalik, Neha January 2013 (has links)
No description available.
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Catalytic cleavage of vegetable oil derivatives to aldehydes and other bio-based building blocks / Coupure catalytique de dérivés d'huiles végétales en aldéhydes et autres plateformes biosourcéesVu, Duc Nam 19 November 2018 (has links)
Les aldéhydes sont des produits chimiques importants dans la synthèse organique, en raison de leurs vastes applications dans les cosmétiques, les produits pharmaceutiques et les herbicides. De plus, ils peuvent être convertis en composés à valeur ajoutée tels que des tensioactifs, des polymères, etc. Classiquement, les aldéhydes sont produits par hydroformylation ou ozonolyse réductrice des alcènes. Cependant, les deux méthodes souffrent de l'utilisation de catalyseurs coûteux et de ligands sophistiqués (hydroformylation) ou de la nécessité d'un procédé à forte intensité énergétique (ozonolyse). En conséquence, le développement d'approches plus durables pour la production d'aldéhydes est hautement souhaitable.Dans ce contexte, nous avons développé deux méthodes pour produire des aldéhydes à partir de dérivés d’acides gras insaturés. La première voie consiste à préparer des a-hydroxycétones grasses à partir de 1,2-diols et les couper pour obtenir des aldéhydes avec de bons rendements. Dans cette voie, deux systèmes catalytiques (homogènes et hétérogènes à base de métaux) ont été développés pour oxyder les diols vicinaux en a-hydroxycétones correspondantes. La coupure de ces espèces a été effectuée par un procédé de rétro-benzoin utilisant des sels de thiazolium thermiquement stables et les aldéhydes ont été récupérés par distillation réactive. La seconde voie repose sur la décomposition des ß-hydroxy hydroperoxydes gras facilement préparés à partir d'oléate de méthyle époxydé. De plus, la décomposition de l'espèce peroxyde a été étudiée dans des conditions thermiques pour donner des aldéhydes. Enfin, la coupure des 1,2-dicétones gras et la valorisation des aldéhydes ont également été étudiés pour conduire aux esters correspondants pouvant être utilisés comme monomères / Aldehydes are important chemicals in organic synthesis, due to their vast applications in cosmetics, pharmaceuticals and herbicides. Moreover, they can be converted to value-added compounds such as surfactants, polymers, etc. Conventionally, aldehydes are produced through hydroformylation or reductive ozonolysis of alkenes. However, both methods suffer from the use of expensive catalyst and sophisticated ligands (hydroformylation) or the requirement of high energy intensive process (ozonolysis). As a result, the development of more sustainable approaches for the production of aldehydes is highly desirable.In this context, we have developed two methods to produce aldehydes from unsaturated fatty acid derivatives. The first route involves the preparation of fatty a-hydroxyketones from 1,2-diols and their cleavage to give aldehydes with good yields. In this route, two catalytic systems (metal-based homogeneous and heterogeneous) have been developed to oxidize vicinal diols to corresponding a-hydroxyketones. The cleavage of these species has been carried out through a retro-benzoin process using thermally stable thiazolium salts and the aldehydes were recovered by reactive distillation. The second route relies on the decomposition of fatty ß-hydroxy hydroperoxides that are easily prepared from epoxidized methyl oleate. Moreover, the decomposition of the peroxide species was studied under thermal conditions to give aldehydes. Finally, the cleavage of fatty 1,2-diketones and the valorization of aldehydes were also studied to give the corresponding esters that could be used as monomers
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Self Condensation Reaction Of Alpha-ketophosphonatesGollu, Mehmet 01 September 2007 (has links) (PDF)
This thesis presents synthesis of tertiary & / #945 / -hydroxy phosphonate derivatives. & / #945 / -Ketophosphonates is known that they are both acyl anion precursors and electrophiles. In this work, & / #945 / -ketophosphonates were used as both acyl anion precursors and electrophiles in the presence of catalytic amount of KCN. & / #945 / -Ketophosphonates underwent benzoin-type condensation reaction.
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