化学学报 ›› 1988, Vol. 46 ›› Issue (7): 679-685. 上一篇    下一篇

研究论文

双环笼状磷酸酯衍生物的研究 I: 1-氧代-4-取代-2,6,7-三氧杂-1-磷杂双环[2,2,2]辛烷衍生物的合成和反应研究

李玉桂;王建基;韩涛;刘云山;曹金鸿;蒋晓春;缪方明;刘晓兰   

  1. 南开大学元素有机化学研究所;中国军事医学科学院;天津师范大学
  • 发布日期:1988-07-15

Study of caged bicyclic phosphates I: 1-Oxo-4-substituted-2,6,7-trioxa-1-phosphabicyclo-[2,2,2] octane and its reactions

LI YUGUI;WANG JIANJI;HAN TAO;LIU YUNSHAN;CAO JINHONG;JIANG XIAOCHEN;MIAO FANGMING;LIU XIAOLAN   

  • Published:1988-07-15

用浓硝酸与钒酸盐氧化1-氧代-4-羟甲基-2,6,7-三氧杂-1-磷杂双环-[2,2,2]辛烷(1)得羟酸2. 对应的酰氯3与一系列酚类或芳胺类反应得新化合物4a-4s. 3与苯二酚、氨基酚或苯二胺反应得化合物5a-5e. 研究了3的反应, 并发现4b在醋酸中经铁粉还原时产物发生O→N酰基重排, 通过元素分析、IB、^1H NMR及部分化合物的MS和X射线衍射分析确定了新化合物的结构. 生物初筛正在进行中.

关键词: 钒酸盐, 铵化合物, 晶体结构测定, X射线衍射分析, 硝酸, 重排反应, 二环辛烷, 氧杂环化合物, 簇状化合物, 农药

1-Oxo-4-hydroxymethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane was oxidized with concentrated nitric acid to the corresponding acid. From the reaction of the acid chloride with various phenols and aryl amines, new bicyclophosphates, e.g. I (R = H, halo, alkyl, NO2, MeO; X = O, NH) were prepared The reduction of I (R = 2-NO2, X = O) with iron powder in HOAc gave the O甆 acyl migration product I (R = 2-OH, X = NH). The elemental anal., IR, 1H NMR, and MS spectra of these new compounds were recorded, and the crystal structure of I (R = 4-MeO, X = NH) was determine by the x-ray diffraction method.

Key words: VANADATE, AMMONIUM COMPOUND, CRYSTAL STRUCTURE DETERMINATION, X-RAY DIFFRACTION ANALYSIS, NITRIC ACID, REARRANGEMENT REACTION, BICYCLOOCTANE, OXYGEN HETEROCYCLICS, CLUSTER COMPOUND, PESTICIDES

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