Nitronates 的轉變

張曜昌

指導教授 ： 姚清發

國立臺灣師範大學/理學院/化學系/碩士(2002年)

摘要

無資料

關鍵字

硝基烷

並列摘要

第一部分
Reactions of trans-β-nitrostyrene 1a with the anion of dimethyl malonate 2a generated the nitronate 3a in THF solution. When 3a was treated with phosphorus trichloride in the presence of DMAP in THF solution or in pyridine solution only, nitroalkane 4a, chlorooxime 5a, and nitrile 6a were isolated (Table 1). When the addition reaction to generate 3a was conducted in THF solution and the transformation of the 3a into final products was conducted in the cosolvent of THF-pyridine solution at room temperature or both reactions were all conducted in THF solution only in the presence of DMAP under refluxing. Only trace of nitroalkane 7a, some of bicyclic product 8a, and little of nitrile 9a were generated when 1a reacted with the anion of dimethyl allylmalonate 2b and then with PCl3 in THF solution under different conditions (Table 4). Similarly, tricyclic product 11a and nitrile 12a also were prepared by reaction of 1a with the anion of dimethyl 3-cyclohexenylmalonate 2c and PCl3. All these results indicate that nitronates can be converted into nitroalkanes, chlorooximes, and nitriles by PCl3 or can be converted into nitroalkanes, polycyclic products, and nitriles by PCl3 in
the presence of dipolarphiles。
第二部分
Reaction of trans-β-nitrostyrene 1a with the anion of dimethyl malonate 2a generated the nitronate 3a in THF solution. Then 3a can undergo cycloaddition and ring opening to generate azodioxides via the intermediate nitroso alkanes. Similarly, 1a also could react with the anion of diethyl allylmalonate or the anion of diisopropyl allylmalonate to generate azodioxides. When 1a reacted with 3-butenyl-magnesium bromide and was workup under similar conditions, only nitroalkane 4e was generated.
At room temperature, azodioxides dissociated to nitroso alkanes, and dimerized to obtain azodioxides again. Azodioxides can transform into oximes in THF solution under refluxing.

並列關鍵字

nitroalkanes