摘要
以溴化四正丁铵为催化剂,在相转移催化条件下以KMnO_4氧化环三(邻亚藜芦基)(Cyclotriveratrylene,简称CTV),得到了CTV-5,10-二酮。经~1H-NMR和X-射线衍射法测定,为一近似的“马鞍”形立体结构。此化合物属正交晶系,空间群为D_(2h)^(25)-Pbca。晶胞参数为a=14.301(3),b=16.411(4),c=24.040(4)(?),V=5642.0(?)~3,F(000)=2400(e),Z=8,Dc=1.33g/Cm^3,μ_(MoKa)=1.1cm^(-1)。用SHELXTL直接法解出,以最小二乘修正。 用稀释法合成了1,10-二氧代-2,9-二氮杂-[10](2,6)-吡啶并环蕃和1,10,17,26-四氧代-2,9,18,25-四氮杂[2]邻环[2](2,6)-吡啶并[2]邻环[2](2,6)-吡啶并环蕃。
CTV-5, 10-dione (Ⅳ) is synthesized by oxidizing cyclotriveratrylene(CTV) with KMnO, under the phase-transfer catalysis condition catalysed by tetrabutylammonium bromide. Its chemical structure is confirmed by elementary analysis, IR, MS, 1H-and 13C-NMR. We have affirmed the, sterical structure of the product to be a similiar 'sad-dle' by X-ray diffraction analysis. The two carhonyl groups ar.e not in the same side of the reference . plan. The crystal of this compound belongs to orthorhombic, the space group is Pbca and the unit cell parameters are a = 14,301(3), b = 16.411(4), c = 24.040(4)A,V = 5642.0A3,F(000)=2400(e),Z = 8,Dc = 1.33 G/cm3, μ(MoKa) = l.1cm-1. The crystal structure is solved by SHELXTL direct method and refined by least-squares method.In addition, two azaphanes l,10-dioxo-2,9-diaza [10] (2,6-pyridinophane(Ⅴ) and 1,10,17,26-tetraoxo-2,9,18,25-tetraaza [2] orthocyclo [2] (2,6) pyridino[2] orthocyclo [2](2,6) pyridinophane(Ⅵ) were synthesized in high diluted solution.
出处
《北京大学学报（自然科学版）》
CAS
CSCD
北大核心
1989年第2期138-145,共8页
Acta Scientiarum Naturalium Universitatis Pekinensis
关键词
环蕃
CTV-5
10-二酮
立体结构
Cyelophane
Cyclotriveratrylene-5, 10-dione
Tetrabutylammonium bromide
Phase-transfer catalysis
2,6-Pyridinedicarbonyl chloride
X-Ray diffraction
1,10 -Dioxo-2, 9-diaza[10](2,6) pyridinophane
1,10, 17, 26-Tetraoxo-2,9,18, 25-tetraaza. [2]
