1,8-azacineole, and the bromination products of dimethyl bicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylate

Derbyshire, Roger Paul Carlos (2003). 1,8-azacineole, and the bromination products of dimethyl bicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylate PhD Thesis, School of Molecular and Microbial Sciences, The University of Queensland.

       
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Author Derbyshire, Roger Paul Carlos
Thesis Title 1,8-azacineole, and the bromination products of dimethyl bicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylate
School, Centre or Institute School of Molecular and Microbial Sciences
Institution The University of Queensland
Publication date 2003
Thesis type PhD Thesis
Supervisor Dr Ray Carman
Total pages 157
Collection year 2003
Language eng
Subjects L
250399 Organic Chemistry not elsewhere classified
780103 Chemical sciences
Formatted abstract This thesis describes two independent projects. The first project comprises the majority of the work in this thesis. The second unrelated project was the final part of a study over many years into the chemistry of bromination.

Project 1 (Chapter 1)

1,8-Azacineole is the nitrogen analogue of 1,8-cineole (a bicyclic monoterpene ether present in the leaves of many Eucalyptus species) and a prospective natural product alkaloid. A sample of 1,8-azacineole was required for GC/MS comparison purposes, but previous literature syntheses of the compound were either low yielding or not successfully reproducible during the current work. A novel synthetic route to 1,8-azacineole from the inexpensive monoterpene diene limonene (in 23-29% overall yield) was thus developed. The extracts of leaves from six Australian Eucalyptus species were analysed by GC/MS but no trace of 1,8-azacineole was detected.

In lead-up work to the final synthetic procedure for 1,8-azacineole, the electrophile-catalysed intramolecular ring closure experiments of 8-amino-p-menth-lene and some of its N-protected (N-benzyl, N-benzoyl, N-acetyl, and N-t-butyloxycarbonyl) derivatives were performed. Some interesting and unexpected results were obtained, including some novel aziridine chemistry. In one example, the N-benzoyl compound was treated with N-bromosuccinimide (NBS) to give a bicyclic dehydrooxazepine with a novel ring system. In other examples, the use of mercury(II) salts led to allylic oxidation products in some cases, as well as a nitrogen heterocycle containing a bicyclo [3.2.1] ring system.

Project 2 (Chapter 2)
The bicyclic diene dimethyl bicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylate was reacted with bromine and the mixture of five isomeric dibromides produced was separated by HPLC. Each compound was fully characterised by 2D NMR spectroscopy and one of the products, a cis-1,2-dibromide, was matched with material from the debromination of a potential cis-dibrominating reagent. This work has been published in The Australian Journal Of Chemistry: R. M. (barman, R. P. C. Derbyshire, K. A. Hansford, R. Kadirvehaj, W. T. Robinson, Aust. J. Chem., 2001, 54,117.
Keyword Essences and essential oils -- Analysis
Alkaloids -- Synthesis

 
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