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The Beckmann and Schmidt rearrangements as an approach to the synthesis of diazabiphenylenes

The Beckmann and Schmidt rearrangements as an approach to the synthesis of diazabiphenylenes

Mendonca, S. (1974) The Beckmann and Schmidt rearrangements as an approach to the synthesis of diazabiphenylenes. MPhil thesis, Thanes Polytechnic.

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Abstract

The Schmidt reaction of cis, trans, cis-tri cyclop, [5,3,0,0 2,6] deca-3,8-dione, a photodimer of cyclopent-2-en-l-one was found to give a mixture of two dilactams. The structure of the major dilactam was established as cis, trans, cis-3, 9-diazatricyclol [6,4,0,0 2,7] dodecane-4, 10-dione on the basis of its spectroscopic properties and those of its N,,N' –dimethyl and N,N'-dibenzyl derivatives.
Single ring expansion of the diketone gave mainly cis, trans, cis
3-azatricyclo [6,3,0,0 2,7] undecane-4,9-dione, and a number of its transformation products are described.
The Beckmann rearrangement of the mixture of dioximes derived from the diketone, also gave a mixture of two dilactams; the major component was established as cis, trans, cis-4,10-diazatricyclo [6,4,0,0 2,7] dodecane-3,9-dione on the basis of its spectroscopic data and those of its N,N'-dimethyl and N,N ! -dibenzyl derivatives. The minor component was found to be identical with that of the other dilactam obtained from the Schinidt reaction and was tentatively assigned as cis, trans, cis-3,10-diazatricyclo-[6,4,0,0 2,7] dodecane-4, 9-dione.
Attempted reduction of the dilactams to the corresponding diamines was not successful but reduction of N,N'-dibenzyl-cis, trans, cis-3, 9-diazatricyclo [6,4,0,0 2,7] dodecane-4, 10-dione gave the corresponding diamine.
Attempted dehydrogenation of the above diamine did not give any diazabiphenylene.

Item Type: Thesis (MPhil)
Uncontrolled Keywords: chemistry
Subjects: Q Science > QD Chemistry
Faculty / Department / Research Group: Faculty of Engineering & Science > Department of Pharmaceutical, Chemical & Environmental Sciences
Last Modified: 17 Oct 2016 09:14
Selected for GREAT 2016: None
Selected for GREAT 2017: None
Selected for GREAT 2018: None
URI: http://gala.gre.ac.uk/id/eprint/14969

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