Triazene derivatives of (1,x)-diazacycloalkanes. Part X. Synthesis and characterization of a series of 1,4-di[2-aryl-1-diazenyl]-trans-2,5-dimethylpiperazines

Abstract

A series of 1,4-di[2-aryl-1-diazenyl]-trans-2,5-dimethylpiperazines(5a–5m), have been synthesized by the reaction of trans-2,5-dimethylpiperazine with two equivalents of the appropriate diazonium salt. The products have been characterized by IR and NMR spectroscopy, and the molecular composition has been verified by high-resolution EI mass spectrometry with accurate mass measurement of the molecular ion. The presence of stereocenters at C2 and C5 of the piperazine ring in the bis-triazene (5) creates two unique pairs of diastereotopic protons in the methylene groups at positions 3 and 6 of the piperazine ring, as evidenced by the complexity of the NMR spectra, which nevertheless can be fully assigned in some cases, such as the anisyl- (5i) and phenyl- (5j) derivatives. The assignment of the proton and carbon signals in the tolyl- derivative (5h) has been aided by the use of 2D NMR HSQC spectroscopy. These results compare favorably with assignments of proton and carbon signals reported previously for triazenes of type 1 and bis-triazenes of types 3 and 4b.