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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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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
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
Authors/Creators:Jaturonrusmee, Wasna
Keywords: Nitrogen compounds, Ring formation (Chemistry)
Copyright Holders: The Author
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Copyright 1989 the Author - The University is continuing to endeavour to trace the copyright
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Additional Information:

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

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