含葑基的缩氨基硫脲、噻二唑的合成、表征与晶体结构

Synthesis, Characterization and Single Crystal Structure of 4-Fenchylthiosemicarbazone and Its Thiadiazole Derivatives

以(-)-葑酮为原料经中间体葑胺合成4-葑基氨基硫脲(4),4与醛缩合得到11个未见文献报道的葑基缩氨基硫脲(5),5用六氰合铁(III)酸钾氧化成环得到相应的2,5-二取代-1,3,4-噻二唑类化合物(6);产物的结构经IR,NMR和元素分析确认,并用X射线衍射法测定化合物6d的晶体结构.化合物6d属单斜晶系,P2(1)空间群,晶胞参数a=1.18719(10)nm,b=1.48814(18)nm,c=1.21629(12)nm,β=118.113(2)°,Mr=343.48,V=1.8953(3)nm3,Dc=1.204Mg/m3,Z=4,λ=0.071073nm,μ(MoKα)=0.181mm-1,F(000)=736.

4-Fenchylthiosemicarbazide （4） was synthesized from （-）-fenchone by a three-step reaction in a yield of 45%. A series of 4-fenchylthiosemicarbazones （Sa-Sk） were obtained by the condensation of 4 with aryl aldehydes in 83%-98% yields. Cyclization of 5 in the presence of Ka[Fe（CN）6] afforded eleven undocumented 2-aryl-5-fenchylamino- 1,3,4-thiadiazoles （6a-6k） in yields of 71%-91%. The structures of 5 and 6 were established on the basis of IR, NMR spectra and elemental analysis, and the structure of 6d was confirmed by X-ray single-crystal diffraction analysis. The crystal of 6d belongs to monoclinic, space group P2（1） with cell parameters a= 1.18719（10） nm, b= 1.48814（18） nm, c= 1.21629（12） nm,β= 118.113（2）°, Mr=343.48, V= 1.8953（3） nm^3, Z=4, Dc=1.204 Mg/m^3, λ=0.071073 nm, μ（Mo Kα）=0.181 mm^-1 and F（000）= 736.