Thesis (M. Phil.)--University of Hong Kong, 1986.

published_or_final_version / Chemistry / Master / Master of Philosophy

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The phototransposition reactions of thiophene- carbonitriles were shown to occur via the intermediate formation and isomerisation of 5-thiabicyclo[2˙1˙0]pent- 2-enes . Thus, irradiation of thiophene-3-carbonitrile in cyclohexane gave 5-thiabieyelo[2˙1˙0]pent-2-ene-2-carbonitrile as the primary photochemical product. Further irradiation produced thiophene-2-carbonitrile. The reaction was reversible, Addition of furan to 5-thiabicyclo[2˙1˙0]pent-2-ene-2- carbonitrile yielded a mixture of exo and endo-10,4-oxa thiatetracyclo[5˙2˙1˙0,sup>2,6</sup>˙ 0sup>3,5</sup>]dec-8-ene-2-carbonitrile. These two adducts were similarly formed upon irradiation of either thiophene-2 or 3-carbonitrile in furan.

The design and synthesis of two heterocyclic thioanalogues of 7-deoxy daunomycinone, 9-acetyl-6,9,11-trihydroxythioxantho{2,3-g}- and -{3,2-g}tetralin, was accomplished. Various synthetic methodologies to accomplish this were evaluated and two key steps necessary for this synthesis were developed. The first consisted of a novel annulative synthetic sequence utilizing a biacetyl synthon, 3,3-diethoxy-2-butanone cyclohexylimine, and an ortho bis-halomethylarene. The second consisted of the use of o-chlorosulfenylbenzoyl chloride as a thiosalicyclic acid equivalent. Model studies toward the further elaboration of these 7-deoxy aglycones to the active glycosides were also studied. / In addition, 1-{{2-{(2-dydroxyethyl)amino}ethyl}amino}-4-hydroxythioxanthone was prepared and found not to have antitumor properties against P-388 leukemia in vivo.

The pyrrolo[3,2,1-ij]quinolin-6-one ring system was synthesised from 3-aryl-4,6-dimethoxyindoles and 2,3-disubstituted-4,6-dimethoxyindoles. The reaction of 4,6-dimethoxyindoles under Friedel-Crafts or Vilsmeier-Haack acylation gave the 2- and 7-indolyldeoxybenzoins in good yield. Cyclisation of 7-indolyldeoxybenzoins with N,N-dimethylformamide dimethyl acetal as a one carbon reagent gave the pyrroloquinolin-6-ones in high yield. Reduction of pyrroloquinolin-6-ones with hydrogen gas and 10% palladium on carbon or lithium aluminium hydride yielded the dihydropyrroloquinolin-6-ones. Demethylation of pyrroloquinolin-6-ones with 48% hydrobromic acid in glacial acetic acid gave a mixture of the monohydroxy and dihydroxy analogues in high yield. The synthesis of quinolin-4-ones using the Conrad-Limpach method was attempted using three different cyclisation conditions such as Dowtherm A, polyphosphoric acid and a mixture of diphenyl ether and methanesulfonic acid. Quinolin-2-ones such as 4-methyl-3-aryl-, 3,4-diaryl- and 3-aryl-4-benzyl-5,7-dimethoxyquinolin-2-ones could be synthesised from either the N-phenylacetylaniline or the N-trifluoroacetyl aniline strategy. Attempted reduction of the quinolin-2-ones with standard metal hydride reagents was unsuccessful. However reduction was achieved via the conversion of quinolin-2-one to the corresponding 2-chloroquinoline followed by reaction of the chloroquinoline with zinc powder and glacial acetic acid to produce a novel, highly substituted quinoline system. Demethylation was successfully carried out with 48% hydrobromic acid in glacial acetic acid to give the trihydroxyquinolin-2-one in high yield. The reactions of 4-substituted-5,7-dimethoxyquinolin-2-ones and the corresponding 2-chloroquinolines as potential organic intermediates were explored. Facile formylation of both quinolin-2-ones and 2-chloroquinolines was observed under Vilsmeier-Haack conditions while acetylation was successful under Friedel-Crafts conditions using antimony (V) pentachloride as the Lewis acid. Further reaction of 8-formyl-quinolin-2-one with 1,2-diaminobenzene in N,N-dimethylformamide led to the formation of a new 8-(benzimidazolyl)-quinolin-2-one ring system. The quinolin-2-ones exhibited selective electrophilic substitution at the C8 position for a range of reactions. However, an unexpected nitration occurred at the C3 position for the 4-methoxy and 4-phenyl-5,7-dimethoxyquinolin-2-ones with good yields. A series of novel 4,6-hydroxylindoles was successfully synthesised from the corresponding methoxy analogues in high yield using anhydrous aluminium chloride. When 3-(4-bromophenyl)-4,6-dimethoxyindole was reacted with 48% hydrobromic acid in glacial acetic acid a 2,2?-indolylindoline dimer was formed. The 5,7-dihydroxyquinolin-2-ones were similarly synthesised in high yield using anhydrous aluminium chloride in chlorobenzene.

Typescript / Includes 3 reprints of articles by the author / Includes bibliographical references / 283 leaves ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Dipyrido[1,2-c:2',1'-e]imidazolium iodide has been syntesised from 2,2'-bipridy and methylene iodide. / Thesis (Ph.D.)--University of Adelaide, Dept. of Organic Chemistry, 1965

vi, 225 leaves : ill. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.) Dept. of Inorganic Chemistry, University of Adelaide, 1969