Synthesis And Properties Of Novel Azo-calix[4] Arene Derivatives With Trizole And Thiadiazole Group

In this paper,designed and synthesized a series of calixarene derivatives.Ap pended azo-group to the upper rim,connected 1-hydroxybenzotrizole and 2-merc apto-5-methyl-1,3,4-thiadiazde to the lower rim of calixarene.The compounds se lectively recognized with different metal cations were investigated by the UV-v is spectra and fluorescence spectra.This paper mainly introduction the dynamic development of calixarene.The development of connectting heteroatom such as three nitrogen triazole and thiadiazde to the lower rim of calixarene have become a focus recently,because the heteroatom is contribution to the chelation with metal cations.Meanwhile import the chromophore,we may get the host molecular with the function of color recognition.The main work of this paper is synthesis and characterize of calixarene derivatives.Main content is as follows:① Sythesis of calix[4]arene,paratert-butyl phenol and formaldehyde through alkylation reaction obtain 5,11,17,23-tetra-t-butyl-25,26,27,28-tetrahydroxycalix[4]arene(Compound A).② Sythesis of 25,26,27,28-tetrahydroxycalix[4]arene(Compound B).Compou nd A with aluminium chloride by reverse Friedel-Crafts alkylation reaction.③ Sythesis of 25,27-bis(2-bromoethoxy)-26,28-dihydroxycalix[4]arene(Comp ound C),Compound B reacted with 1,2-dibromoethane by selective etherisation.④ Compound C reacted with different amines to achieve a series of azo-calix[4]arene derivatives,respectively to form 5-(phenyl-azo)-25,27-bis(2-bromoet hoxy)-26,28-dihydroxycalix[4]arene(Compound D),5-[(3-nitrophenyl)azo]-25,27-bi s(2-bromoethoxy)-26,28-dihydroxycalix[4]arene(Compound E),5,17-bis[(4-nitrop henyl)azo]-25,27-bis(2-bromoethoxy)-26,28-dihydroxycalix[4]arene(Compound F),5-[(4-methoxyphenyl)azo]-25,27-bis(2-bromoethoxy)-26,28-dihydroxycalix[4]arene(Compound G).⑤ Compound D,E,F,G reacted with 1-hydroxybenzotrizole and 2-mercapto-5-methyl-1,3,4-thiadiazde to obtain 5-(phenyl-azo)-25,27-bis[2-(1-benzotriazole)ox oethoxyl]-26,28-dihydroxycalix[4]arene(Compound H)and 5-(phenyl-azo)-25,27-b is[2-(5-methyl-2-thiadiazole)thioethoxyl]-26,28-dihydroxycalix[4]arene(Compound I);5-[(3-nitrophenyl)azo]-25,27-bis[2-(1-benzotriazole)oxoethoxyl]-26,28-dihydroxyc alix[4]arene(Compound J)and 5-[(3-nitrophenyl)azo]-25,27-bis[2-(5-methyl-2-thia diazole)thioethoxyl]-26,28-dihydroxycalix[4]arene(Compound K);5,17-bis[(4-nitro phenyl)azo]-bis[2-(1-benzotriazole)oxoethoxyl]-26,28-dihydroxycalix[4]arene(Comp ound L);5-[(4-methoxyphenyl)azo]-25,27-bis[2-(1-benzotriazole)oxoethoxyl]-26,28-dihydroxycalix[4]arene(Compound M)and 5-[(4-methoxyphenyl)azo]-25,27-bis[2-(5-methyl-2-thiadiazole)thioethoxyl]-26,28-dihydroxycalix[4]arene(Compound N).⑥ All of the products are characterized by IR,1H-NMR,13C-NMR and ESI-MS.⑦ The recognition of compound H-N with metal ions and anions were i nverstigated maingly by UV-vis spectra and fluorescence spectra.The result in dicated that L was highly selective for CO32-over other ions,which leads toobvious color change from light yellow to blue that can be detected by naked eyes.The last is the conclusion of the paper and discussion of further research direction.