Virginia Tech
Radical additions of hydrocarbons, ethers and acetals to alkenes via allyl transfer reaction: A new chain reaction for C-H bond functionalization
Abstract
dc:description.abstractFunctionalization of hydrocarbons via a free-radical based allyl transfer reaction using various allyl bromide substrates has been previously studied. The work described in this dissertation focuses on the replacement of Br by phthalimido-N-oxyl (PINO ) which helps make this chemistry environmentally friendly. To replace Br with PINO , replacement of previously used allyl-bromide substrates with new allyl-PINO substrates were necessary. Various allyl- PINO compounds were synthesized and the use of these allyl-phthalimido-N-oxyl (allyl-PINO) compounds for the functionalization of various alkyl aromatic hydrocarbons is demonstrated. Kinetic studies were performed to observe the efficiency of the new chain reaction compared to the previously reported studies with allyl-bromides. We recently discovered that these allyl substrates are useful for the functionalization of ethers and acetals. The functionalization of various cyclic and acyclic ethers was performed using these allyl transfer reactions. This reaction was also performed in-solution, which allowed us to perform these reactions at low reagent concentrations. Kinetic chain lengths were measured for these reactions. High chain lengths were observed for all used ethers. Kinetic studies to investigate the rate of radical addition-elimination processes were performed using laser flash photolysis and competition kinetics. These experiments helped us to measure the reactivity and selectivity of PINO as a chain carrier in comparison with Br. Additionally, a new competition experiment was designed to study the relative rate constant for the 􀈕-fragmentation process. For this experiment a novel substrate that contains two leaving groups, Br and PINO, was synthesized, and the relative rates of elimination of Br vs PINO were compared.
Degree
thesis:*- Name thesis:degree_name
- Ph. D.
- Level thesis:degree_level
- doctoral
- Discipline thesis:degree_discipline
- Chemistry
- Department dc:contributor.department
- Chemistry
- Grantor dc:publisher
- Virginia Tech
- Year dc:date.issued
- 2013
Author and committee
dc:creator, dc:contributor.*- Author dc:creator
-
- Patil, Shradha Vasant
- Chair dc:contributor.committeechair
-
- Tanko, James M.
- Committee members dc:contributor.committeemember
-
- Carlier, Paul R.
- Brewer, Karen J.
- Castagnoli, Neal Jr.
Subjects
dc:subject × 5Rights
dc:rights- Statement dc:rights
-
- In Copyright
- Licence dc:rights.uri
Identifiers
dc:identifier.*- Dc Identifier Other
- vt_gsexam:718
- OAI identifier oai:identifier
- oai:vtechworks.lib.vt.edu:10919/50658