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Title: Synthetic studies on nitrogen heterocycles
Author: McGuigan, Henry
ISNI:       0000 0001 3624 577X
Awarding Body: University of Glasgow
Current Institution: University of Glasgow
Date of Award: 1986
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Part 1 Treatment of the chlorohydrin (49), of the Reissert compound, 2-acetyl-l-cyano-1,2-dihydroisoquinoline (48) with sodium ethoxide gives 1-ethoxy-3-methylisoquinoline-4-carbaldehyde (50) and highly coloured by-products. A deep purple compound has been isolated from the reaction mixture, and identified as ethyl 2-amino-1-oxo-inden-3-carboxylate (51). This first example of a simple 2-amino-indenone has been synthesised from ethyl homophthalate. Attempts were made to find an alternative synthetic route using indanone and 2-methyl-2-nitrosopropane. Several chlorohydrin alkyl ethers, 2-benzoyl-4-chloro-1-cyano-3-ethoxy-1,2,3,4-tetrahydroisoquinoline (27), and the corresponding 3-methoxy compound (28) were prepared from Reissert compound, 2-benzoyl-1-cyano-1,2-dihydroisoquinoline (2). The stereochemistry of these ethers was investigated. With triethylamine there was a 1,4-elimination of hydrogen chloride to give reactive intermediates (29) and (30), respectively, which were trapped as Diels-Alder adducts (83) and (84) with N-phenylmaleimide. The stereochemistry of these adducts was determined using 1H n. m. r. nuclear Overhauser enhancement spectra. Other Reissert compounds and their derivatives have been studied briefly. Part 2 Oxidation of benzyl N-hydroxycarbamate, PhCH2OCONHOH (55a), with sodium periodate in the presence of cyclopentadiene gave the cycloadduct (87a) of the transient dienophile, benzyl C-nitrosoformate, PhCH2OCONO (56a), and the diene.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Organic chemistry