Three main areas of work were investigated during the course of this research project, as outlined below: A general strategy for the synthesis of (aryl)alkylsulfonic acids (aryl being defined as triphenylene, 130, pyrene, 83, and perylene, 92) has been developed which utilized Sonogashira cross-coupling and Strecker displacement reactions on readily available aromatic templates. Using this approach the synthesis of sodium triphenylene-2-sulfonate, 128, sodium 10-(triphenylen-2-yl)dec-9-yne-1-sulfonate, 15, sodium 10-(triphenylen-2-yl)decane-1-sulfonate, 16, sodium 10-(pyren-1-yl)dec-9-yne-1-sulfonate, 18, sodium 10-(pyren-1-yl)decane-1-sulfonate, 19, sodium 3,3â-((pyrene-1,6-diylbis(dec-9-yne-10,1-diyl))bis(sulfanediyl))bis(propane-1-sulfonate), 136 and sodium 4-(perylen-3-yl)butane-1-sulfonate, 31 was accomplished. The CuAAC click reaction of pyrene- and perylene-derived azides proved to be effective for the synthesis of triazole-based sulfonic acids which also incorporated carbocyclic aromatic cores. The synthesis of sodium (1-(pyren-1-ylmethyl)-1H-1,2,3-triazol-4-yl)methanesulfonate, 48, sodium/potassium 6-((1-(pyren-1-ylmethyl)-1H-1,2,3-triazol-4-yl)methoxy)naphthalene-2-sulfonate, 51, sodium 4-((1-(pyren-1-ylmethyl)-1H-1,2,3-triazol-4-yl)methoxy)benzenesulfonate, 54, sodium (1-(4-(pyren-1-yl)butyl)-1H-1,2,3-triazol-4-yl)methanesulfonate, 50, sodium 4-((1-(4-(pyren-1-yl)butyl)-1H-1,2,3-triazol-4-yl)methoxy)benzenesulfonate, 56, sodium/potassium 6-((1-(4-(pyren-1-yl)butyl)-1H-1,2,3-triazol-4-yl)methoxy)naphthalene-2-sulfonate, 53, sodium (1-(4-(perylen-3-yl)butyl)-1H-1,2,3-triazol-4-yl)methanesulfonate, 64, sodium 4-((1-(4-(perylen-3-yl)butyl)-1H-1,2,3-triazol-4-yl)methoxy)benzenesulfonate, 68, sodium/potassium 6-((1-(4-(perylen-3-yl)butyl)-1H-1,2,3-triazol-4-yl)methoxy)naphthalene-2-sulfonate, 66 and sodium (1-(10-(perylen-3-yl)dec-9-yn-1-yl)-1H-1,2,3-triazol-4-yl)methanesulfonate, 70 using this methodology is reported. Finally, the synthesis of 4,10-dichlorochrysene, 74, from 1,5-dihydroxynapthalene, 73, using a four-step benzannulation procedure (the BHQ reaction), was re-investigated. This basic protocol was also extended to the synthesis of 4,10-dibromochrysene, 75, albeit in low yield. The application of this methodology to the synthesis of 4,10-difluorochrysene, 76, proved to be capricious and not suitable for the synthesis of bulk quantities of these materials.
| Date of Award | 31 Dec 2023 |
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| Original language | English |
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| Awarding Institution | - The University of Manchester
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| Supervisor | Peter Quayle (Supervisor) & Stephen Yeates (Supervisor) |
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