1-氧代-4(取代)-2,6,7-三氧杂-1-磷杂双环[2,2,2]辛烷晶体结构研究

CRYSTAL AND MOLECULAR STRUCTURE OF 1-OX0-4-(SUBSTITUENT)-1-PHOSPHA-2,6,7-TRIOXACYCLO(2, 2, 2)OCTANE

具有双环笼状结构的磷酸酯类化合物的合成始于60年代。由于其分子呈高度对称的笼状结构及其衍生物具有很强的生物活性而且作用机理独特,引起人们普遍的关注。某些衍生物可用作杀菌剂,杀螨剂,除草剂,灭火剂,树脂稳定剂等等.由于此类化合物的生理作用机理不同于常用的有机磷农药.因此,可能会成为潜在的农药新途径。对此类化合物的晶体结构的测定,至今只有有限文献报导,为了研究其分子结构与化学性质及生物活性的关系,本文分析了四个磷氧杂双环磷酸酯类化合物的晶体结构,其合成方法已有报导。

The crystal structure of four 1-oxo-4-(substituent)-1-phospha-2,6,7-trioxacyclo(2,2,2) octane have been determinded by dimention single-crystal X-ray analysis. All intensity data were collected with an Enraf-Nonius CAD4 diffractometer,using graphite monochromated Cu-K_α radiation and ω/2θ scan, and corrected for LPand emperical absorption factors. All crystal structures were solved by MULTAN andrefined by full matrix least-squares with lsotropic thermal vibration factors for Hand anisotropic for the others. Crystal data, (Ⅰ)X=NH, R=H, C_(11)H_(12)O_5NP, monoclinic, P2_1/n, α=5. 821 (1),b=11.613(3), c=17.508(6)A, β= 92.31(3)°, V=1182.6A^3, Z=4, D_c=1. 519g·cm^(-3), 1489 unique reflections(I>3σ) R=0. 038, R_w= 0. 040; (Ⅱ) X=NH,R= ρ-OCH_3, C_(12)H_(14)O_6NP, monoclinic P2_1/n, α=10. 145(3), b=12. 246(4), c=11. 609(3) A, β=115. 99(3)°, V=1297. 5A^3, Z=4, D_c=1. 53g·cm^(-3), 1859unique reflections(I>3σ), R=0. 057, R_w=0. 061; (Ⅲ)X=O, R=ρ-OCH, C_(12)H_(13)O_7P, monoclinic P2_1/c,α=5.949(2), b=11.069(3), c=19. 183(4)A, β=97. 05(3)°, V=1253. 5A^3, Z=4,D_c=1. 59g·cm^(-3), 1072 independent reflections(I>3σ), R=0. 047, R_w=0. 053; (Ⅳ)X=O, R=o-NO, C_(11)H_(10)O_8NP, orthorhombic, P2_12_12_1, α=6. 055(4), =b11. 173(2),c=18. 579(3)A, V=1256. 8A^3, Z=4, D_c=1. 67g·cm^(-3), 938 unique reflections(I>3σ), R=0.052, R_w=0.058.