Interaction of β-Cyclodextrin Catalyst with p-Chlorobenzonitrile for the Synthesis of 5-Substituted 1H-tetrazoles in n,n-Dimethylformamide：a DFT Study  

作　　者：YI Shan-Feng WAN Ya-Li WANG Xue-Ye 易山峰;万娅莉;王学业(key laboratory for green organic synthesis and application of hunan province,key laboratory of environmentally friendly chemistry and applications of ministry of education,college of chemistry,xiangtan university,Xiangtan,Hunan 411105,China)

机构地区：Key Laboratory for Green Organic Synthesis and Application of Hunan Province, Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, College of Chemistry, Xiangtan University, Xiangtan, Hunan 411105, China

出　　处：《Chinese Journal of Structural Chemistry》2018年第10期1523-1532,共10页结构化学（英文）

基　　金：supported by the Scientific Research Fund of Hunan Provincial Education Department(No.12A132)

摘　　要：The synthesis of 5-substituted 1H-tetrazoles in n,n-dimethylformamide（DMF） with b-cyclodextrin（β-CD） as catalyst can get an excellent yield in short reaction time.The interaction of β-CD with p-chlorobenzonitrile plays an important role in this process.This paper studies the complex of β-CD with p-chlorobenzonitrile using density functional theory（DFT） method.The minimum energy structure is investigated in water,DMF and DMSO.Hydrogen bonds are researched on the basis of natural bonding orbital（NBO） analysis.The relative position between p-chlorobenzonitrile and β-CD in DMF is confirmed by 1H nuclear magnetic resonance（1H NMR）.The data from 13 C and 15 N spectra indicate that more positive charges focus on the carbon atom of cyanogroup（C11） and more negative charges concentrate on the nitrogen atom of cyanogroup（N12） upon complexation.The results from frontier molecular orbitals and Mulliken charge reveal that β-CD catalyst improves the reactivity and electrophilicity of p-chlorobenzonitrile.Meanwhile,the functional group of p-chlorobenzonitrile is easier to be attacked by azide ions in the presence of β-CD as catalyst.

关 键 词：β-cyclodextrin（β-CD） density functional theory（DFT） CATALYST inclusion complex p-chlorobenzonitrfle 

分 类 号：O643.36[理学—物理化学] O626[理学—化学]