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Synthesis and properties of some nitrogen-containing bridged systems

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Jaturonrusmee, Wasna (1991) Synthesis and properties of some nitrogen-containing bridged systems. PhD thesis, University of Tasmania.

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Abstract

The general aims of this work were to develop routes to new nitrogen-containing
bridged systems and to study the properties of these and related known
systems. Firstly attention was directed to the synthesis of some new 3-aza-naphthothiadiazolophanes
by a ring destruction involving the cyanogen bromideand
chloroformate ester-mediated cleavage of a central benzylic carbon-nitrogen
bond in cyclic amines containing a reduced isoquinoline moiety, with the
concomitant loss of a proton to generate the final aromatic ring system. This type
of approach provided a convenient and direct route to 3-aza-naphthothiadiazolophane
derivatives as presented in Chapter 2.
Secondly, studies on the effects of aromatic ring distortion on the
chemical properties of some highly strained 3-aza [5]- and 3-aza [6](1,7)-
naphthalenophanes were undertaken as described in Chapter 3. These
naphthalenophanes underwent Diels-Alder addition as dienes, and in some cases as
dienophiles, to afford a number of new heterocyclic bridged derivatives with a
variety of functionality. The addition occurred exclusively on the nonmethoxylated
ring under mild conditions for naphthalene derivatives. Very rapid
cycloaddition was noted with the most highly distorted 3-aza [51(1,7)-
naphthalenophane system. Kinetic studies on the Diels-Alder reaction of the 3-
aza [5]- and 3-aza [6](1,7) naphthalenophanes with maleic anhydride were
undertaken. These reactions were found to be second order; the rate constants,
activation energies, enthalpies and entropies of activation were also determined and
found to be consistent with the reaction type proposed.
Thirdly, use of the 3-aza( 1,7) naphthalenophane derivatives as
precurors for the synthesis of larger bridged systems was investigated (Chapter 4).
Studies on the use of a bridged derivative as a potential precursor for a 3-
aza [9] metacyclophane derivative by a bromine-induced C-C cleavage reaction are
described. The successful synthesis of a 3-aza [9] metacyclophane derivative by
oxidative cleavage of a 3-aza [6](1,7) naphthalenophane derivative was achieved. Finally, approaches to the construction of some 3-aza [5] (1,8)-
anthracenophane derivatives by ring destruction with cyanogen bromide and
methyl chloroformate were investigated. To this end, routes to the synthesis of
isoquinoline-fused pentacyclic precursors were studied. Results of these efforts
are discussed in Chapter 5. Although the desired precursors were not realized, a
number of new synthetic areas have been opened up as a result of the work,
involving new 2,8-bridged isoquinoline derivatives and a fused β- lactam
derivative.
In all the work, extensive use was made of ¹H and ¹³C n.m.r.
spectroscopy in particular, in assigning structures to products.
As a result of these studies, a number of new 3-aza-phane derivatives
were obtained. The development of synthetic routes to a number of new
heterocyclic systems and some interesting chemical properties in strained 3-
aza (1,7) naphthalenophane derivatives have also been established. In all,
representatives of eighteen new bridged heterocyclic systems have been made,
providing a wider basis for future structure-property relationship studies.

Item Type: Thesis (PhD)
Keywords: Nitrogen compounds, Ring formation (Chemistry)
Copyright Holders: The Author
Copyright Information:

Copyright 1989 the Author - The University is continuing to endeavour to trace the copyright
owner(s) and in the meantime this item has been reproduced here in good faith. We
would be pleased to hear from the copyright owner(s).

Additional Information:

Includes bibliographical references. Thesis (Ph.D.)--University of Tasmania, 1991

Date Deposited: 19 Dec 2014 02:27
Last Modified: 29 Nov 2016 02:57
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