两个环己烷螺含氮杂环化合物的合成和晶体结构

Synthesis and Structure of Two Heterocyclic Compounds 1,2,4,5-Tetraazaspiro[5,5] undecane-3-thione and 1,2, 4-Triazaspiro-[4,5]decane-1-ene-4-amino-2-thione

环己酮与硫代碳酰肼在不同介质中的反应，合成出两个不同的环己烷螺含氮杂环化合物。经Ｘ－射线结构分析确定它们分别为１，２，４，５－四氮螺［５，５］十一烷－３－硫酮，Ｃ＿７Ｈ＿（１４）Ｎ＿４Ｓ（Ⅰ）和１，２，４，－三氮螺［４，５］癸－１－烯－４－氨基－３－硫酮。Ｃ＿７Ｈ＿（１２）Ｎ＿４Ｓ＿ｘ（Ｓ＿ｘ＝０．８Ｓ＋０．２Ｏ）（Ⅱ）。晶体学参数分别为（Ⅰ）：Ｐ２＿１／ｃ，ａ＝１２．０２６（４），ｂ＝２６．８１７（６），ｃ＝１２．０４２（３），β＝１１５．９４（２）°，Ｚ＝４，Ｖ＝９３３．４（１０），Ｍ＿ｒ＝１８６．２８；（Ⅱ）：Ｐ２＿１／ｍ，ａ＝６．５９５（７），ｂ＝６．８１７（６），ｃ＝１０．５７２（６），β＝１０６．３（１）°，Ｖ＝４５６（１），Ｚ＝２，Ｍ＿ｒ＝１８１．０５。最终一致因子分别为Ｒ＝０．０５４，Ｒ＿ｗ＝０．０６５和Ｒ＝０．０８９，Ｒ＿ｗ＝０．０９６。两个化合物中，环己烷都为椅式构型，它与其螺联的６员氮杂环，５员氮杂环的最小二乘平面间的夹角分别为６８．９４和９０°。并对合成反应途径作了初步讨论。

The four compounds were prepared by the reaction of cyclohexanone with thiocarbohydrazide, and they were characterized by IR. MS and UV.The crystal structure of the title compounds were determined by X-ray diffraction.C_7H_(14)N_4S,M_r= 186.28,space group P2_1/c,Cell parameters: a= 12. 026(4),b=6.817 (6),c= 12. 042(3),β=115.94(2)°,Z= 4,V=933.4(10};C_7H_(12)N_4S_x(S_x= 0.85+0. 2O),M_r= 181. 05,space group 934.P2_1/m.a= 6.595935.(7),b=6.817(6),c=10.572(6), β=106. 3(1)°,V=456(1),Z=2. The final R=0.054,0. 089,R_w=0. 065,0.096,respectively.The dihedral angles of the least-squares planes of six-membered ring or five-membered ring and corresponding cyclohexane of chair-form in two compounds are 68. 94 and 90°,respectively. In addition,the possible reaction schemes were discussed.