Reaction of bis(triphenylphosphine)chlorocobaltaindane-1,3-dione with 1 equivalent of AgBF(,4) followed by treatment with various ligands resulted in the formation of cationic phthaloylcobalt complexes. Reaction of these cationic complexes with alkynes produced naphthoquinones. Comparison of the structure and reactivity of various cationic cobalt complexes led to several important conclusions regarding the mechanistic nature of the quinone forming reaction. These conclusions were used as a guide in the design of a neutral phthaloylcobalt complex featuring a diequatorially coordinated dimethylglyoxime ligand which was found to give high yields of substituted 1,4-naphthoquinones on treatment with functionalized alkynes. Addition of 1 equivalent of CoCl(,2)(.)6H(,2)O was found to significantly increase the reaction rate of the neutral cobalt complexes. / The information obtained from reaction studies of the phthaloyl-cobalt complexes was applied to several maleoylcobalt complexes in order to develop an organotransitionmetal approach to benzoquinone synthesis. In order to generalize such a synthetic route, a general synthesis of substituted cyclobutenediones adaptable to the synthesis of multigram quantities of dione was developed. This synthesis was based on a cyclo-addition reaction of dichloroketene with vinyl sulfides. The resulting cycloadducts underwent an unusual elimination-readdition sequence resulting in the formation of 4-thiophenyl-2-chlorocyclobut-2-ene-1-ones which on oxidation with MCPBA underwent a {2,3}sigmatrophic shift to afford substituted cyclobutenediones. Several of these diones were converted to maleoyl dimethylglyoxime complexes which gave good yields of substituted benzoquinones on treatment with alkynes. / Source: Dissertation Abstracts International, Volume: 45-01, Section: B, page: 0185. / Thesis (Ph.D.)--The Florida State University, 1984.
| Identifer | oai:union.ndltd.org:fsu.edu/oai:fsu.digital.flvc.org:fsu_75267 |
| Contributors | BAYSDON, SHERROL LEE., Florida State University |
| Source Sets | Florida State University |
| Detected Language | English |
| Type | Text |
| Format | 189 p. |
| Rights | On campus use only. |
| Relation | Dissertation Abstracts International |
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