Synthesis, properties, and applications of polynitro- and polyamino(2.2)paracyclophanes

摘要

The synthesis, properties, and uses of polynitro- and polyamino (2.2) paracyclophanes and the electrochemistry of 1,3,5-tris(phenylamino)benzenes were investigated. The dinitro (2.2) paracyclophanes were synthesized by dimerization of 2-nitro-p-quinodimethane, which was generated by a 1,6-Hofmann elimination, and by direct nitration of (2.2) paracyclophane and 4-nitro (2.2) paracyclophane. Both synthetic procedures gave significant increases in yields over the known synthetic procedure to form dinitro (2.2) paracyclophanes. Anti-5,8,13,16-tetramethyl-4,7,12,15-tetranitro (2.2) paracyclophane and anti-5,8,13,16,21,24,29,32-octamethyl-4,7,12,15,20,23,28,31-octanitro (2.2.2.2) -paracyclophane were obtained from the dimerization and tetramerization of 3,6-dimethyl-2,5-dinitro-p-quinodimethane generated by a 1,6-Hofmann elimination. The diamino (2.2) paracyclophanes were synthesized by the catalytic hydrogenation of the appropriate dinitro (2.2) paracyclophane. The energetic properties of the polynitro (2.2) paracyclophanes were investigated by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC) and it was demonstrated that the products of the dimerization, tetramerization, and polymerization of 3,6-dimethyl-2,5-dinitro-p-quinodimethane decompose catastrophically, releasing energies comparable to known explosives.;The electronic properties of the polynitro (2.2) paracyclophanes, polyamino (2.2) paracyclophanes, and 1,3,5-tris(phenylamino)benzenes were investigated electrochemically by cyclic voltammetry (CV). The electrochemistry of para-substituted 1,3,5-tris(phenylamino)benzenes showed a linear relationship between their oxidation potentials and the $rmsigmasb{psp{+}}$ Hammett values of the substituents. A variety of potential uses for the diamino (2.2) paracyclophanes were demonstrated by the formation of the electroactive poly(pseudo-para-4,12-diamino (2.2) paracyclophane), the stable $rm N,N,Nspprime,Nspprime$-tetramethyl-pseudo-para-4,12-diamino (2.2) paracyclophane radical cation, poly(p-xylidene-pseudo-para-4,12-diamino (2.2) paracyclophane), and pseudo-ortho-N,N$sp prime$-bissalicylidene-4,12-diamino (2.2) paracyclophane copper(II) catalyst for cyclopropanation of olefins with diazoacetate. The possible applications of these compounds were also discussed.