Some reactions of norcaranylidene with polar solvents
dc.contributor.author | Chu, I-Shan | |
dc.contributor.department | Chemistry | |
dc.date | 2018-08-15T08:43:22.000 | |
dc.date.accessioned | 2020-07-02T06:04:32Z | |
dc.date.available | 2020-07-02T06:04:32Z | |
dc.date.copyright | Wed Jan 01 00:00:00 UTC 1986 | |
dc.date.issued | 1986 | |
dc.description.abstract | <p>As part of our efforts to understand the chemistry of cyclopropylidenes in solution, the reactions of norcaranylidene in alcohols and nitriles have been studied;In alcohols (methanol or t-butanol), the partitioning of norcaranylidene between intramolecular insertion and intermolecular reaction with alcohols is a function of alcohol concentration. In methanol, an ylide intermediate is transformed into the product ether in a stepwise manner. However, in t-butanol, the corresponding ylide intermediate releases the t-butanol molecule to give the intramolecular insertion product, in competition with protonation to form the ether product;Methanol was found to react with norcaranylidene 2.5 times faster than t-butanol, irrespective of the total alcohol concentrations. A reasonable interpretation of the activation parameters is that norcaranylidene is solvated preferentially by t-butanol monomers at "high" alcohol concentration, but is solvated essentially equally by either methanol or t-butanol at "low" alcohol concentration. Thus at either "low" or "high" alcohol concentrations, the "starting carbene" is a single, albeit differently, solvated species;When nitriles are present in methanol, the nitrile ylide intermediate from the reaction norcaranylidene with nitriles reacts with methanol to yield a mixture of epimeric methanol insertion products. In acrylonitrile, the ylide is also captured by another molecule of acrylonitrile to give a 3 + 2 cycloadduct. And dipolarophiles also capture the diazo-precursor to norcaranylidene in acrylonitrile and methacrylonitrile;Pyrolysis of anti-7-bromo-syn-7-trimethylstannylbicyclo 4.1.0 heptane also generates norcaranylidene. This allows the high temperature study of the kinetic deuterium isotope effects for the reaction of norcaranylidene with methanol and t-butanol. Mechanisms to account for the isotope effects at low (diazo-precursor) and high (tin bromide precursor) temperatures are discussed. Two changes in mechanism are seen as the temperature is changed from -78(DEGREES) to 160(DEGREES)C.</p> | |
dc.format.mimetype | application/pdf | |
dc.identifier | archive/lib.dr.iastate.edu/rtd/8064/ | |
dc.identifier.articleid | 9063 | |
dc.identifier.contextkey | 6328938 | |
dc.identifier.doi | https://doi.org/10.31274/rtd-180813-13108 | |
dc.identifier.s3bucket | isulib-bepress-aws-west | |
dc.identifier.submissionpath | rtd/8064 | |
dc.identifier.uri | https://dr.lib.iastate.edu/handle/20.500.12876/81011 | |
dc.language.iso | en | |
dc.source.bitstream | archive/lib.dr.iastate.edu/rtd/8064/r_8627099.pdf|||Sat Jan 15 02:05:39 UTC 2022 | |
dc.subject.disciplines | Organic Chemistry | |
dc.subject.keywords | Chemistry | |
dc.subject.keywords | Chemistry | |
dc.subject.keywords | Organic | |
dc.title | Some reactions of norcaranylidene with polar solvents | |
dc.type | article | |
dc.type.genre | dissertation | |
dspace.entity.type | Publication | |
relation.isOrgUnitOfPublication | 42864f6e-7a3d-4be3-8b5a-0ae3c3830a11 | |
thesis.degree.level | dissertation | |
thesis.degree.name | Doctor of Philosophy |
File
Original bundle
1 - 1 of 1
No Thumbnail Available
- Name:
- r_8627099.pdf
- Size:
- 4.04 MB
- Format:
- Adobe Portable Document Format
- Description: