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

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.

Level dc:type.qualificationlevel

mphil

Grantor dc:publisher.institution

Thanes Polytechnic

Year dc:date.issued

1974

Author dc:creator

• Mendonca, S.

Advisor dc:contributor.advisor

• Rogers, V.

• QD Chemistry

Language dc:language

en