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Title: 酮胺配位基化合物:合成、鑑定和開環聚合(II)
Ketiminate Complexes: Synthesis, Characterization, and Ring-Opening Polymerization (II)
Authors: 黃瑞賢
Contributors: 化學系
Keywords: 仳各;C−N 鍵的斷裂及生成;
Pyrrole;Phenyl isocyanate;C−N bond breaking and formation;Aluminum
Date: 2003
Issue Date: 2012-12-10T01:41:03Z
Publisher: 行政院國家科學委員會
Abstract: 化合物[C4H3N(CH2NMe2)-2]AlMe2 (1) 可經由 [C4H4N(CH2NMe2)-2]與 1 當量之 AlMe3 於二氯
甲烷中反應而得。 化合物1 與 1 當量之PhNCO 於甲苯中反應而得2. PhNCO 可插入鋁及二甲基
胺氮原子之間的鍵,並且經C−N 鍵的斷裂及生成而引發一種不尋常的重排反應。
[C4H4N(CH2NMe2)-2] 與 1 當量之PhNCO 於乙醚中反應生成具有仳各取代之尿素衍生物3。
AlMe3 與 1 當量之 3 於二氯甲烷中反應得O-鍵結 與 N-鍵結之二甲基鋁化合物 4a 和 4b. 4a
和4b 均可經由1H NMR 光譜測得,但是其相對比例則與所使用之氘溶劑有關 。
[C4H3N(CH2NMe2)-2]AlMe2 (1) is prepared by the reaction of substituted pyrrole [C4H4N(CH2NMe2)-2]
with 1 equiv of AlMe3 in methylene chloride. Reaction of complex 1 with one equiv of phenyl
isocyanate in toluene generates complex 2. The phenyl isocyanate was inserted into the aluminum and
dimethylamino nitrogen bond and induced an unusual rearrangement which results the C−N bond
breaking and formation. The reaction of substituted pyrrole [C4H4N(CH2NMe2)-2] with 1 equiv of
phenyl isocyanate in diethyl ether yields a pyrrolyl attached urea derivative 3. The reaction of AlMe3
with 1 equiv of 3 in methylene chloride afforded O-bounded and N-bounded aluminum dimethyl
complexes 4a and 4b. Both 4a and 4b are observed in 1H NMR spectra, however, the relative ratio of
4a and 4b depends on the deuterium solvent used.
Relation: 國科會計畫, 計畫編號: NSC92-2113-M018-007; 研究期間: 9208-9307
Appears in Collections:[Department of Chemistry] NSC Projects

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