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. Copyright © 1990 Journal of Heterocyclic Chemistry