Use this URL to cite or link to this record in EThOS: https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.471059
Title: Aspects of the synthesis of polycyclic thianes and related systems
Author: Routledge, William
ISNI:       0000 0001 3538 4567
Awarding Body: University of Glasgow
Current Institution: University of Glasgow
Date of Award: 1978
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Abstract:
The acid-catalysed acetylation of bicyclo [3.3.1] nonan-2,6-dione (79) and its 9-thia and 9-oxa analogues (165 and 187) is described. In the presence of toluene-p-sulphonic acid or low concentrations of concentrated sulphuric acid, O-acetylation occurred to produce mixtures of the corresponding mono- and bisenol acetates. At higher sulphuric acid levels, C-acetylation was favoured, 79 and 165 producing adamantane and 2-thiaadamantane derivatives respectively while 187 yielded the doubly C-acetylated species (202). The attempted dehydrochlorination of 2,6-dichloro-9-thiabicyclo-[3.3.1] nonane (161) with pyridine failed to produce an olefinic product but yielded instead the bispyridinium salt (215). Reaction of chloroalkene (213) with pyridine at room temperature gave monopyridinium salt (216) which underwent facile structural rearrangement at elevated temperatures (>50) to give a mixture of 216 and 225. Pyrolytic elimination of pyridine hydrochloride from 215 and 216 proceeded with structural rearrangement furnishing 9-thiabicyclo [4.2.1] nona-2,4-diene (229). In order to prepare 8-thiabicyclo [3.2.1] octane derivatives as potential precursors to thia- analogues of biologically active tropane alkaloids, the condensation of sulphur dichloride with cycloheptadienes (238, 282, 286 and 292) was investigated. Cyclohepta-2,6-dienone (238) and its ethylene ketal (292) reacted with SCI2 in an identical regiospecific manner to produce the unsymmetrical 1:1 adducts (307 and 305) while 1-benzoyloxycyclo-hepta-3,5-diene (286) gave the expected symmetrical dichloride (295) Cyclohepta-3,5-dienone (282) reacted with SCl2 with the elimination one equivalent of hydrogen chloride furnishing the photosensitive allylic chloride (301) which was further dehydrochlorinated to 8-thiabicyclo [3.2.1]octa-3,6-dien-2-one (303).
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID: uk.bl.ethos.471059  DOI: Not available
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