Studies On Synthesis Of Calix[6]arene Nitro Derivative And Complex With TNT And RDX

The macrocyclic compound calixarene is formed by the phenol unit connected with methylene on the ortho-position of the phenol hydroxyl, which is the third generation super molecular compound following cyclodextrin and crown ether because the size of its cavum , the conformations and the substitutions on the up rim or low rim are all controllable. The complexes formed by calixarene and RDX,TNT maybe meet the need of detonator industry, because they will have advantages both on passivation and on high-octane.At first, A calix[6]arene precursor with tert-butyl groups on benzene rings was synthesi zed by a condensation of p-tert-butylphenol and formaldehyde with KOH as catalyst in a yield of 84.72 %. The influence of catalyst quantity, reaction time, reflux temperature was discussed.Then the tert-butyl groups was removed off by a reverse Friedel-Crafts reaction, calix[6]arene was obtained with no substitution in the opposite position of the phenol hydroxyl in a yield of 71.23 %. The structure of the target products were characterized by IR and 1H-NMR spectrum.Secondly, p-nitro-calix[6]arene was synthesized by two different methods.â‘´Calix[6]ar ene was heated in H₂SO₄ for 4h at 80℃, and then treated with 61% HNO₃, the yield is 14.87%;⑵p-nitro-calix[6]arene was gained in the yield of 18.90% when p-tert-butyl-calix[6]arene was treated with H₂SO₄(98%)/HNO3(65%)(6 to 1). The structure of the products was characterize- ed by IR and 1H-NMR.Finally, the complex properties of p-tert-butylcalix[6]arene and TNT, p-tert-butylcali- x[6]arene and RDX in solution were investigated by fluorescence spectrum, respectively. The experiment results showed that when the p-tert-butylcalix[6]arene is added into the solution of TNT, RDX, fluorescence spectrum and UV spectrum all shift towards long wavelength, and the intensities increas obviously, all of these indicate that the complexes are formed between p-tert-butylcalix[6]arene and RDX, and between p-tert-butylcalix[6]arene and TNT. At last, investigated the steady constant and the ratio of p-tert-butylcalix[6]arene and RDX, p-tert-butylcalix[6]arene and TNT in complexes by fluorescence spectrum and UV spectrum. The ratio of p-tert-butylcalix[6]arene and RDX is 1to1, the steady constant is 325.70; the ratio of p-tert-butylcalix[6]arene and TNT is 1to1, the steady constant is 3119.90.