12-(2-氯苯基)-7,11,13,16-四氧杂二螺[5.2.5.2]十六烷的合成和结构研究

Synthesis and Crystal Structure of 12-(2-Chlorophenyl)-7,11,13,16-tetraoxaspiro[5.2.5.2]cetane

邻氯苯甲醛与季戊四醇反应得到中间体5,5-二(羟甲基)-2-(2-氯苯基)-1,3-二氧六环(1),1再与环己酮反应生成12-(2-氯苯基)-7,11,13,16-四氧杂二螺[5.2.5.2]十六烷(2).反之,先用环己酮与季戊四醇反应生成9,9-二(羟甲基)-7,11-二氧杂螺[5.5]十一烷(3),3再与邻氯苯甲醛反应也可生成标题化合物2.化合物1和2的结构用X射线单晶衍射、元素分析和核磁共振氢谱进行了确定.X射线单晶衍射晶体结构表明化合物1属单斜晶系,空间群为P2(1)/n,晶体学参数:a=0.56768(15)nm,b=0.9807(3)nm,c=2.1785(6)nm,a=90°,β=90.204(4)°,γ=90°,V=1.2128(5)nm3,Z=4,Dc=1.417Mg/m3,μ=0.315 mm-1,F(000)=544.化合物2也属于单斜晶系,空间群为C2/c,晶体学参数:a=1.5894(5)nm,b=1.5704(4)nm,c=2.8369(9)nm,a=90°,β=101.103(5)°,γ=90°,V=6.948(4)nm3,Z=16,Dc=1.296 Mg/m3,μ=0.237mm-1,F(000)=2880.

12-（2-Chlorophenyl）-7,11,13,16-tetraoxaspiro[5.2.5.2]cetane （2） was prepared by cyclohexanone and 5,5-bis（hydroxymethyl）-2-（2-chlorophenyl）-l,3-dioxane （1） which synthesized from the reaction of the o-chlorobenzaldehyde and pentaerythriol, or prepared by o-chlorobenzaldehyde and 9,9-bis（hydroxymethyl）-7,11-dioxaspiro[5,5]undecane （3） which synthesized from the reaction of the cyclohexanone and pentaerythriol. Compounds 1 and 2 were characterized by X-ray diffraction, elemental analysis, 1H NMR. Single crystal X-ray diffraction analyses reveal that compound 1 belongs to monoclinic system with space group P2（1）/n with a=0.56768（15）nm,b=0.9807（3）nm,c=2.1785（6）nm,α=90°,β=90.204（4）°,γ=90°,V=1.2128（5）nm3,Z=4,Dc=1.417Mg/m3,p=0.315mm,F（000）=544. Compound 2 also belongs to monoclinic system with space group C2/c with a=1.5894（5）am,b=1.5704（4）nm,c=2.8369（9）nm,α=90°,β=101.103（5）°,γ=90°,V=6.948（4）nm3,Z=16,Dc=1.296Mg/m3,μ=0.237mm-1,F（000）=2880.