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Chemistry

Theses/Dissertations

Photochemistry

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Articles 61 - 64 of 64

Full-Text Articles in Physical Sciences and Mathematics

Photochemical Generation And Intramolecular Chemistry Of 2-Hydroxy-2-Methylpropylidene, Robin Farlow May 2001

Photochemical Generation And Intramolecular Chemistry Of 2-Hydroxy-2-Methylpropylidene, Robin Farlow

Honors Theses

2-(1a,9b-Dihydro-lH-cyclopropa[l]phenanthren-1-yl)-propan-2-ol was synthesized by two different but related synthetic routes and characterized by melting point, IR GC/MS, CHN, and NMR spectroscopy. Photolysis of the alcohol in benzene d-6 led to the formation of 2-butanone, 1-methylcyclopropanol, and 2,2-dimethyloxirane in a 26:10:1 ratio via 2-hydroxy-2methylpropylidene, a novel ?-hydroxycarbene. These products are a consequence of intramolecular insertions of the carbene into C-C, C-H, and O-H bonds. Molecular orbital calculations performed at the Becke-3LYP/6-31G(d) level indicate that the singlet form of this carbene is more thermodynamically stable than the triplet. Furthermore, the transition states to the three products from the singlet species were modeled …


A Study Of The Photolysis Of O-Methyl Podocarpinitrile Oxide, Dianne Marie Hunter Jan 1980

A Study Of The Photolysis Of O-Methyl Podocarpinitrile Oxide, Dianne Marie Hunter

Dissertations and Theses

The photolytic reaction of 0-methyl podocarpinitrile oxide to yield the δ-lactam (shown below) was studied under various conditions such as: solvent (hexane, methanol), mercury lamp wattage (lOOW, 450W), filter (Pyrex, Corex, Vycor), and additives (dichloromethane, hexafluorobenzene). The reactions were analyzed with IR, NMR and HPLC. Preparative medium pressure liquid chromatography and TLC were used in the δ-lactam isolation. The conditions resulting in the optimum yield of δ-lactam were determined. The photolytic stability of the δ-lactam under the conditions in which it was formed indicated that it was relatively stable only in hexane.


A Photochemical Study Of S-Triazolo[4,3-B] Pyridazine And 3-Diazo-4-Oxo-3,4-Dihydroquinoline, John Timothy Carlock Aug 1977

A Photochemical Study Of S-Triazolo[4,3-B] Pyridazine And 3-Diazo-4-Oxo-3,4-Dihydroquinoline, John Timothy Carlock

Theses and Dissertations

When subjected to ultraviolet radiation in the presence of an alkene, s-triazolo[4,3-b]pyridazine (STP) undergoes an unusual 3 + 2 photocycloaddition wherein the alkene adds to the 1 and 8 positions of STP with concommitant N4-N5 bond cleavage yielding 5,6-disubstituted-6,7-dihydro-7-methylene (and 7-cyanomethyl)-5H-pyrrolo[1,2-b]-s-triazoles. Amides and esters of indole-3-carboxylic acid have been synthesized by a novel reaction employing the ultraviolet irradiation of 3-diazo-4-oxo-3,4-dihydroquinoline (QDA) in the presence of amines or alcohols respectively. QDA, when irradiated, is postulated to undergo an internal Wolff Rearrangement to Indole-3-ketene which can add any amine or alcohol to form the corresponding amide or ester in modest to good …


The Photoreduction Of Indigo Carmine Flavin Mononucleotide And Diphosphopyridine Nucleotide, By Illuminated Chloroplasts, M. Odell Hobbs Apr 1958

The Photoreduction Of Indigo Carmine Flavin Mononucleotide And Diphosphopyridine Nucleotide, By Illuminated Chloroplasts, M. Odell Hobbs

Theses and Dissertations

An investigation was made of the photoreduction of indigo carmine dye and flavin mononucleotide (FMN) by an illuminated sugar beet leaf homogenate in the presence of 2,6-dichlorophenolindophenol dye (DPIP) and ascorbic acid. DPIP and ascorbate were absolutely required for the reaction. Reconstitution experiments indicated a requirement for a heat-labile factor present in the supernatant fluid following centrifugation of the leaf homogenate. This factor activated the photoreduction of indigo carmine more than 20 times. The photoreduction of FMN was activated 2 times by this factor. Studies on the stoichiometry of indigo carmine photoreduction revealed that one mole of ascorbate was photooxidized …