Chemistry of hydrazine adducts of bicyclo [3.3.1] nonadiene diones and an approach to the synthesis of some bridged heterocyclic annulenes

Pathirana, Ranjith Nandalal (1982) Chemistry of hydrazine adducts of bicyclo [3.3.1] nonadiene diones and an approach to the synthesis of some bridged heterocyclic annulenes. University of Southampton, Doctoral Thesis.

Record type: Thesis (Doctoral)

Abstract

The literature concerning polyamines and some bridged cyclic amines of biological importance is reviewed. The structure of the dihydrazone 4,9dimethyl-2,3,7,8-tetraazatetracyclo[7.3.1.0.4,1206,10]trideca-l,6-dieneprepared by the reaction of hydrazine with 4,8-dimethylbicyclo[3.3.1]nona3,7-diene-2,6-dione was established. This hydrazone has two double bonds at bridgehead positions (anti Bredt). The reduction of 4,9-dimethyl-2,3,7,8-tetraazatetracyclo[7.3.1.0.4,1206,10]trideca-l,6-diene to give the dihydrazine 1,6-dimethyl-2,3,7,8-tetraazatetracyclo[7.3.1.0.4,1206,10]tridecane was investigated. Reduction of the dihydrazone using lithium aluminium hydride and aluminium chloride gave the dihydrazine but lithium aluminium hydride alone or aluminium chloride alone induced the ring cleavage of the dihydrazone to afford tricyclic dihydro pyrazoles. The oxidation of the dihydrazine and reaction with aldehydes were also examined. The oxidation gave the bridged bisazoalkane 1,6-dimethyl-2,3,7,8-tetraazatetracyclo[7.3.1.0 4,1206,10]trideca-2,7-diene and the reactions of the dihydrazine with aldehydes gave products with further cyclisation. In Part Two, the literature of bridged heterocyclic annulenes is reviewed. Aspects of the chemistry of the readily available bridged l,5-benzodiazepine 4,6-dimethyl-5,2,8-ethanylylidene-5H-1,9-benzodiazacycloundecine are described. The allylic bromination of this bridged 1,5-benzodiazepine gave the dibromide 4,6-dibromomethyl-5,2,8-ethanylylidene-5H-1,9-benzodiazacycloundecine in good yield. Transformations of this dibromide by a series of nucleophiles gave products with formation of extra carbocyclic rings, and extra heterocyclic rings with incorporation of one or two further nitrogen groups. The chemistry of these bridged systems was extensively studied and led to a synthesis of a benzo[14] annulene.

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