Skip navigation

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.

[img]
Preview
PDF
S. Mendonca 1974 - secured.pdf - Published Version
Available under License Creative Commons Attribution Non-commercial No Derivatives.

Download (4MB) | Preview

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

Actions (login required)

View Item View Item

Downloads

Downloads per month over past year

View more statistics