Metal-Directed Synthesis of Dithia Diaza Macrocycles Carrying Pendant Alcohol and Also Nitro or Carboxylate Groups

Abstract

Copper(II)-directed condensation of 1,9-diamino-3,7-dithianonan-5-ol with nitroethane or di-ethyl malonate yields (6-methyl-6-nitro-1,11-dithia-4,8-diazacyclotetradecan-13-ol)copper(II) and (diethyl 13-hydroxy-1,11-dithia-4,8-diazacyclotetradecane-6,6-dicarboxylate)copper(II) respectively in good yields, with the latter readily converted by decarboxylation into the complex of ethyl 13-hydroxy-1,11-dithia-4,8-diazacyclotetradecane-6-carboxylate. Analogues without the alcohol group based on 3,7-dithianonane-1,9-diamine are also described. The pendant alcohol group fused directly to a macrocyclic ring carbon can act as an axial donor group, as illustrated in the X-ray crystal structure analysis of (diethyl 13-hydroxy-1,11-dithia-4,8-diazacyclotetradecane-6,6-dicarboxylate)copper(II) perchlorate . This complex crystallizes in the P2₁/c space group, a 12.650(3), b 8.620(1), c 24.382(4) Ǻ, β 96.10(2)°. The copper ion lies in a distorted square-based pyramidal environment of two sulfur donors (average Cu-S 2.338 A), two nitrogen donors (average Cu-N 2.035 Ǻ) and the pendant alcohol donor [Cu-O 2.319(6) Ǻ], with the copper ion displaced slightly (0.043 Ǻ) out of the macrocycle donor plane towards the pendant alcohol donor.