Arene imine derivatives of chrysene and of benzo[g]chrysene: 1a,11c-dihydrochryseno[5,6-b]azirine and 1a,13c-dihydrobenzo[11,12]chryseno[5,6-b]azirine

The syntheses of the K-iraines (which are also benzo-bay-region derivatives) of chrysene (1) and benzo[g]-chrysene (2) are described. The preparation of 1a,11c-dihydrochryseno[5,6-b]azirine (5) was accomplished by treatment of 1a,11c-dihydrochryseno[5,6-b]oxirene (4) with sodium azide, and the mixture of trans-azido-alcohols 6 and 7, so formed, was either cyclized with triethyl phosphite, or converted into E-6-azido-5-chloro-5,6-dihydrochrysene (8) followed by lithium aluminium hydride reduction. The synthesis of 1a,13c-dihydrobenzo-[11,12]chryseno[5,6-b]azirine (12) included the transformation of the corresponding oxide 11 into a mixture of E-9-azido-9,10-dihydrobenzo[g]chrysen-10-ol (13) and E-10-azido-9,10-dihydrobenzo[g]chrysen-9-ol (14), and reaction with tri-n-butylphosphine to give a mixture of Staudinger adducts 15 and 16 that underwent thermal decomposition into 12 upon heating in boiling dichloromethane.