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
Pre-2014 Departments:	Thames Polytechnic Thames Polytechnic > School of Chemistry
Last Modified:	25 Jul 2019 15:46
URI:	http://gala.gre.ac.uk/id/eprint/14969

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