反式硫代环磷酰基硫脲的合成及性质研究

采用反式２－异硫氰式－４－基基－５，５－二甲基－２－硫代－１，３，２－二氧磷杂环己烷与不同胺的加成反应合成了１３个的反式环状硫代磷酰基硫脲衍生物，生物活性初步测试表明，部分化合物具有杀菌及植物生长调节活性，本文首次报道了２－氯－苯基－５，５－二甲基－２－硫代－１，３，２－二氧磷杂环己烷与硫氰酸钾反应的立体化学。     

Conformational and configurational analysis of 2-phenoxy-2-oxo-1,3,2-dioxaphosphorinanes. Conformational and configurational dependence upon conformation of the diol precursor

Diastereomeric 5-tert-butyl-4-methyl-2-phenoxy-2-oxo-1,3,2-dioxaphosphorinanes were synthesized, and studied by NMR and computational methods in order to determine their predominant conformations as well as their relative configurations. The study was performed assuming a novel criteria, in which, the conformation and configuration of the diastereomeric 5-tert-butyl-4-methyl-2-phenoxy-2-oxo-1,3,2-dioxaphosphorinanes depend upon the conformation of the corresponding diol precursors. In other words, the orientation or pseudo orientation of the groups into the ring framework of the heterocyclic is initially acquired by the direct phosphorylation reaction with the diol precursor in the most stable conformation, and then, once the heterocyclic is formed, the final conformation is dictated by stereoelectronic and steric effects.     

不对称环磷酸肟酯的合成和生物活性研究

通过反式-2-氯-2-氧-4-苯基-5,5-二甲基-1,3,2-二氧磷杂环己烷(Ⅱ)和α-氰基-芳基甲醛肟(Ⅰa-Ⅰf)在相转移催化条件下反应,制得新型的1,3,2-二氧磷杂环磷酸肟酯(Ⅲa_Ⅲf),产物中的非对映异构体经¹HNMR、³¹PNMR和单晶X射线衍射确证.但化合物Ⅱ与芳基甲醛肟反应,得到芳基甲腈和环磷酸,这可能是生成不稳定的环磷酸醛肟酯(Ⅳ)经Beckmann裂解所致.生物活性测试表明,化合物cis-Ⅲd具有很好的抗烟草花叶病毒活性.