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 benzog]-chrysene ( 2 ) are described. The preparation of 1a,11c-dihydrochryseno5,6-b]azirine ( 5 ) was accomplished by treatment of 1a,11c-dihydrochryseno5,6-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]chryseno5,6-b]azirine ( 12 ) included the transformation of the corresponding oxide 11 into a mixture of E-9-azido-9,10-dihydrobenzog]chrysen-10-ol ( 13 ) and E-10-azido-9,10-dihydrobenzog]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.