A mechanistic study of heteroatom di-pi-methane systems containing silicon and nitrogen /
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| Other Authors: | , |
| Format: | Thesis Book |
| Language: | English |
| Published: |
[College Station, Tex.] :
Krochmal,
1976.
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| Subjects: | |
| Online Access: | Link to ProQuest copy Link to OAKTrust copy |
| Abstract: | A series of substituted divinylsilanes: dimethyl-distyryl-(11). Triphenyl-stryrl-(12), diphenyl-distyryl(13), have been prepared for photochemical study. The results of low conversion photolyses of the di-methyl-di-styrylsilane (11) are interpreter in terms of mechanisms for (pi)-bond isomerization which do not pass through a diradical intermediate resulting from C2-C4 carbon-carbon bridging. We have also found that di-(pi)-methane like reaction pathways for these systems are inefficient. It seems likely that the different photochemical reactivity of the di-(pi)-silanes and their carbon analogs is due to the ability of silicon to destabilize the first bridged diradical intermediate along the reaction coordinate or the transition state, 170, for a one step process in which C2-C4 bonding interactions are required. In addition, a series of 1-vinyl-2-pyridone: 1-(2-methyl-1-propenyl)-(14), 1-trans-(2-phenylethenyl)-(15), 1-trans-(1-propenyl)-(16), 1-(E-2-methyl-2-carbomethoxylethenyl)-(17), 1-(5,5,-dimethyl-3-cyclohex-2-en-1-only)-18, have been synthesized by novel sequences. The spectral and photochemical properties of these compounds, (proton and carbon nmr, uv, ir, mass spec) which contain the di-(pi)-amine moiety, have been explored. We have found that the nitrogen-vinyl carbon bond conformation in 1-vinyl-2-pyridones is governed by both electronic and steric factors with the "bisected conformer" predominating.. |
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| Item Description: | "Major Subject: Chemistry." Vita. |
| Physical Description: | x, 186 leaves : illustrations ; 28 cm |
| Bibliography: | Includes bibliographical references (leaves 123-127). |