The Synthesis Of Halogenated Triazole And Halogenated Tetrazole

Triazoles and tetrazoles play an important role in the nitrogen-containing heterocycliccompounds. Due to their special physiological and pharmacological activities, they arewidely used in the fields of medicines and pesticides. Both the nitrogen content and heat offormation of triazoles and tetrazoles are very high, combined with other good overallperformance, they are also favorites in energy materials. The introduction of halogen notonly can active the nitrogen-containing heterocyclic, but also can facilitate the modificationof triazoles and tetrazoles, therefore the halogenated triazoles and tetrazoles are importantintermediates for the synthesis of other functional compounds.The research progress about the applicationes of triazoles and tetrazoles and thesynthesis methords of halogenated triazoles and tetrazoles were reviewed firstly, then thehalogenation reactions of single-triazole and single-tetrazole without substituent group werestudied based on the previous work of predecessors and our group, several halogenatedtriazole and tetrazole compounds were synthesized and their structures were identifiedthrough a variety of methods. At the same time, the reactivities of halogenated triazoles andtetrazoles were further researched.The chlorination reaction of triazole and tetrazole without substituent group werestudied.1H-1,2,4-triazole and1H-tetrazole were synthesized first and then used as rawmaterial to react with sodium dichloroisocyanurate (SDIC) utilizing the reactive of C-Hbond in the azole ring to give the3(5)-chloro-1,2,4-triazole and5-chlorotetrazole. Thestructures of the resulting products were identified through the methods of IR, EI-MS,ESI-MS,1H-NMR,13C-NMR and X-ray single crystal diffraction. The experimental resultsconfirm that SDIC can be used as chlorinated agents of triazole and tetrazole withoutsubstituted group. This method have simple process and mild conditions and easy tooperate and to get raw material.The iodination reaction of triazole and tetrazole without substituent group werestudied. Iodine chloride, as iodine reagent, react with1H-1,2,4-triazole and1H-tetrazole togive the3(5)-iodio-1,2,4-triazole and5-iodiotetrazole, respectively. The structures of theresulting products were identified through the methods of IR, EI-MS, ESI-MS,1H-NMR and13C-NMR.The reactivities of chlorotriazole and chlorotetrazole were disscussed. First,5-chlorotetrazole-2N-oxide was synthesized through two different routes:(1)chlorotetrazole react with oxone directly;(2)5-amino-tetrazole, as substrate, react withoxone after undergo a series of processes including diazotization, nitration, chlorination andneutralization. The structures of the resulting products were identified through the methodsof IR, EI-MS, ESI-MS,1H-NMR,13C-NMR and X-ray single crystal diffraction. The firstroute have simple process and mild conditions and easy to get raw material.Then,3,3’-dichloro-4,4’-azo-1,2,4-triazole, as starting material, react with methylalcohol directly to give3,3’-dimethoxy-4,4’-azo-1,2,4-triazole, and its structure wasidentified through the methods of IR, EI-MS, ESI-MS,1H-NMR,13C-NMR, elementalanalysis and X-ray single crystal diffraction.The crystal structure of five compounds were obtained in this paper, among which5-clorotetrazole,5-chlorotetrazole-2N-oxide and3,3’-dimethoxy-4,4’-azo-1,2,4-triazolehaven’t seen in the literature at present.