Syntheses of novel annelated dihydropyrenes from a common aryne intermediate and interpretation of their proton NMR data

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dc.contributor.author Zhou, Pengzu
dc.date.accessioned 2018-06-19T23:08:15Z
dc.date.available 2018-06-19T23:08:15Z
dc.date.copyright 1990 en_US
dc.date.issued 2018-06-19
dc.identifier.uri https://dspace.library.uvic.ca//handle/1828/9477
dc.description.abstract The existence of the reactive intermediate trans-10b,10c-dimethyl-10b,10c-dihydropyr-1-yne, 57, generated via dehydrobromination, was proved by trapping with N,N-diethyl-1,3-butadienylamine, furan and a series of isoannelated furans. Comparison of 57 with benzyne, 1, was implemented using the results of MMX/PCMODEL calculations. A fast route to annelated dihydropyrenes was developed via the reactive intermediate 57. Through this route, five annelated dihydropyrenes, namely, trans-14b,14c-dimethyl-14b,14c-dihydronaphtho (2,1,8-gra) naphthacene, 204, trans-16b,16c-dimethyl-16b,16c-dihydrobenzo (a) naphtho (2,1,8-fgh) naphthacene, 206a, trans-16b,16c-dimethyl-16b,16c-dihydrobenzo (a) naphtho (2,1,8-hij) naphthacene, 206b, trans-14b,14c,18b,18c-tetramethyl-14b,14c,18b, 18c-tetrahydrodinaphtho (2,1,8-uva; 2,1,8-jkl) pentacene, 224a, and trans-15b,15c,18b,18c-tetramethyl-15b,15c,18b, 18c-tetrahydrodinaphtho (2,1,8-uva; 2,1,8-pon) pentacene, 224b, and one bridged oxa (17) annulene, namely, trans-11b,11c-dimethyl-11b,11c-dihydropyreno (1,2-c) furan, 222, were synthesized. Metal complexation of the benzo (a) dihydropyrene 95 was investigated. This led to the first two metal dihydropyrene complexes, namely, (7,8,9,10,10a,10b-η6)-trans-12b,12c-dimethyl-12b,12c-dihydrobenzo (a) pyrenechromium(0)-tricarbonyl, 239, and (1,2,3,3a-η4) -trans-12b,12c-dimethyl-12b,12c-dihydrobenzo (a) pyreneiron(0)tricarbonyl, 209. The delocalization effects due to complexation were studied. Combining the results of the newly synthesized annelated dihydropyrenes with previously obtained ones, a series of correlations between theoretical calculations and experimental results, such as bond order vs. chemical shift, bond order vs. coupling constant, and ring current vs. chemical shift were devised. The ortho-metalation of dihydropyrene derivatives and synthesis of 1-bromo-2-fluoro-dihydropyrene were attempted. This led to two new dihydropyrene derivatives, namely, trimethylacetamino-trans-10b,10c-dimethyl-10b,10c-dihydropyrene, 99, and 2-diethylcarbamyl-trans-10b,10c-dimethyl-10b,10c-dihydropyrene, 109, and two new cyclophane derivatives, namely, syn-5-bromo-6-fluoro-9,18-dimethyl-2,11-dithia (3.3) metacyclophane, 131a, and anti-5-bromo-6-fluoro-9,18-dimethyl-2,11-dithia (3.3) metacyclophane, 131b. en_US
dc.language English eng
dc.language.iso en en_US
dc.rights Available to the World Wide Web en_US
dc.subject Benzene en_US
dc.subject Synthesis en_US
dc.subject Reactivity en_US
dc.subject Aromatic compounds en_US
dc.title Syntheses of novel annelated dihydropyrenes from a common aryne intermediate and interpretation of their proton NMR data en_US
dc.type Thesis en_US
dc.contributor.supervisor Mitchell, Reginald H.
dc.degree.department Department of Chemistry en_US
dc.degree.level Doctor of Philosophy Ph.D. en_US
dc.description.scholarlevel Graduate en_US

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