Synthesis and nitration of calix[4] (aza) crowns

Calix[4](aza) crowns containing amide groups 3a-d were synthesized by the r eactions of calix[4]arene (1a) or p-tert-butylcalix[4]arene (1b) with N,N'- ethylenebis(2-chloroacetamide) (2a) or N, N'-1,2-phenylenebis(2-chloroaceta mide) (2b) by one step procedure in yields of 85-90%. Calix[4](aza) crowns 4a-b could be obtained by the reduction of 3a-b with LiAlH4 in yields of 51 and 67%, respectively. The nitration of 3a or 3c afforded new chromogenic calix[4]arenes 5a bearing two nitrophenol moieties and 5c bearing one nitro phenol and one quinone moiety, respectively. The ipso-nitrations of 3b and 3d were also studied. Bath gave the products containing one nitrophenol and one quinone moiety. Moreover, a very interesting calix[4]arene derivative Sd containing one cyclohexadienone moiety was also separated as the main pr oduct when 3d was ipso-nitrated.