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

AbstractCalix[4] (aza) crowns containing amide groups 3a—d were synthesized by the reactions of calix[4]arene (la) or p‐tert‐butylcalix[4]arene (1b) with N, N′‐ethylenebis(2‐chloroacetamide) (2a) or N, N′‐ 1,2‐ethylenebis (2‐chloroacetamide) (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‐nitration's of 3b and 3d were also studied. Both gave the products containing one nitro phenol and one quinine moiety. Moreover, a very interesting calix[4]arene derivative 5d containing one cyclohexadienone moiety was also separated as the main product when 3d was ipso‐nitrated.