【作者】 张晓梅；

【导师】 王道全；

【作者基本信息】 中国农业大学 ， 农药学， 2003， 博士

【摘要】 近年来，由于磷杂环化合物在分子识别，超分子化学，不对称催化和生命科学方面的应用而受到重视。本论文对八、十一、十四、十六、二十四员磷氧杂环化合物从化学和生物活性上进行研究，取得了以下结果： 1．对本实验室在研究[1，3，2]-二氧磷杂八环合成过程中尚存疑虑的两个反应进行了系统研究： （1） 确定了6-氯-6-硫-12H-双苯并[1，3，2]-二氧磷杂八环在三乙胺存在下与正丙醇于甲苯中的反应为水解反应，并发现三乙胺存在下，它只与乙醇、正丙醇进行酯化反应。 （2） 研究6-烷氧基-6-硫-12H-双苯并[1，3，2]-二氧磷杂八环与DMSO反应的机理，认为是先水解，再氧化，并将研究结果拓展成由硫代磷酸酯及二硫代磷酸二酯制备磷酸二酯的新方法。 2．合成了具有较好溶解性的三个系列（A、B、C）共9个新双苯并[1，3，2]-二氧磷杂八环衍生物，其结构经³¹P NMR，¹H NMR，¹³C NMR，元素分析，IR及MS确证。 3．研究了四种新α，ω-双羟基化合物D、E、F、G的合成及其与PSCl₃，P₂S₅的关环反应，成功地获得了下列五个中间体H、J、L、O、S，其结构经¹H NMR,¹³C NMR，元素分析，IR及MS确证，还得到了单晶X—射线分析的证实。 单晶X—射线分析结果表明：十四、十六及二十四员化合物为结构基本对称的不规则环，而十一员环则是一个高度不对称的环；十四、二十四硫代磷酰氯可与三氯甲烷形成1∶1的结晶复合物，而十四员磷氧杂二硫代磷酸二酯三乙胺盐L与三氯甲烷形成1∶2的结晶复合物。所有复合物中，三氯甲烷均处于环的孔穴之外。 4．合成了19个新十一、十四、十六、二十四员环磷氧杂硫代磷酰胺衍生物（I、K、P、T），所有化合物结构经NMR，IR，元素分析等手段确证，部分化合物进行了MS测定。 CI。IQ NRIR，CI Y‘。CI nIS、－“”“l“W 卜‘。uri OH＿＿。八＿－＿＿＿、＿s 一J－P～ O（CH、＼O丁 丁CI。IM－w爿／引几，几 CI＼ ／／O（CHZ）flO 11 CIThot‘－“”“W－ C二＼＼／“一N卜IR，／＿广飞CM rOCI4，CH，O n．－／Yn／un＿＼、n”ey＿＿、＿，W ／LI一 飞丁 一。一。－Ll、广”t“”训”C以卜0《CH一hy－／Y 四 人L下／AS CI 一’O。’厂！二．P lied 11一L，riled 一＿NRIRZ t＝IP．lied — — 5．对新八员问 个）环及十一、十四、二十四员磷氧杂硫代磷酸胺衍生物问 个)进行了杀菌及植物生长调节活性粗筛，结果显示，生物活性微弱。磷氧杂环化合物的结构活性关系还需要进一步研究。 6．对十一、十四、十六、二十四元等四个系列磷氧杂硫代磷酸胺及十四元磷氧杂二硫代磷酸酯三乙胺盐 L与某些金属离子 Li＼ Na＼ K、Mgh和 Coh的复合性质进行了初步研究。结果表明，十四元磷氧杂二硫代磷酸酯三乙胺盐可与COC12形成配合物，二十四元磷氧杂硫代磷酸胺可能具有与C。C12形成超分子化合物的能力。更多还原

【Abstract】 In recent years, heterocyclic compounds containing phosphorus have been paid attentions due to their applications in molecular recognition, supermolecular chemistry, chiral catalyst and life science. In this dissertation, eight-, eleven-, fourteen-, sixteen and twenty-four-membered heterocyclic compounds containing phosphorus and oxygen were studied and the results are showed as follow.1. Two reactions occurring in the process of synthesis of 12H-dibenzo[d,g][l,3,2]-dioxa phosphocin derivates were studied systematically.(1)The reaction of 6-chloro-2,4,8,10-tetrachIoro-12H-dibenzo [d,g][l,3,2] dioxaphosphocin-6-sulfide (2a) with n-PrOH in intoluene under refluxing in the present of triethylamine was proved to be hydrolysis process, and in the present of triethylamine, the esterification of 2a with only ethanol and n-propanol can go smoothly.(2) A new way to prepare phosphate diesters from thiophosphate ester and di-thiophosphate diester was discovered in the process of studying the reaction of 6-alkoxy-2,4,8,10- tetrachloro -12H-dibenzo[d,g] [l,3,2]-dioxa phosphocin-6-sulfide with DMSO, and the reaction mechanism can be described as two steps: hydrolysis and then oxidation.2. Three series of nine new12H-dibenzo[d,g][l,3,2]-dioxaphosphocin derivates(A,B,C) with good solubility were prepared. Their structures were confirmed by 31P NMR, 1H NMR, 13C NMR, elemental analysis, IR and MS.3. After preparing four new a,w-diols (D, E, F and G), novel eleven-, fourteen-, sixteen and twenty-four-membered heterocyclic thiophoshosphoryl chloride (H, J, O, S) were synthesized successfully by means of ring-closure reaction of D, E, F, G with PSC13, respectly, and a new fourteen-membered di-thiophosphate diester triethylamide salt L was synthesized also. Their structures were confirmed by X-ray diffraction analysis except 1H NMR, 13C NMR, elemental analysis, IR and MS.The X-ray diffraction analysis showed that fourteen-, sixteen- and twenty-four- members heterocycles are of almost symmetry unregulated cycles and eleven-membered heterocycle is of a highly asymmetry structure. Fourteen- and twenty-four-membered thiophosphoryl chloride form complex with chloroform at ratio of 1:1 but fourteen-membered di-thiophosphate diester triethylamide salt L at ratio of 1:2. The chloroform lies out of the cavity of mother molecular.4. Nineteen new eleven-, fourteen-, sixteen and twenty-four-membered thiophosphoryl amides (I1-6, K1-6, P1, T1-6)were prepared. Their structures were confirmed by 31P NMR, 1H NMR, 13C NMR, elemental analysis and IR, some of them by MS also.5. New compounds were tested as germicide and plant growth regulators, and results showed their low bioactivities. The relations between structure and bioactivity need investigating further.6. Preliminary studying on the complex performance of H, J, O, S and L with metal cations Li+, Na+, K+, Mg2+, Co2+ were carried out. The results showed that L forms complex with CoCl2 and twenty-four-membered may form super molecular compound with更多还原