The synthesis and some reactions of a series of “skipped” polyacetylenes containing terminal acetylene groups
作者:D.A. Ben-Efraim、F. Sondheimer
DOI:10.1016/0040-4020(69)80026-8
日期:1969.1
The synthesis and some reactions of a series of linear 1,4-polyynes containing terminal acetylene groups (Ia–e) are described. Reaction of propargyl bromide (II) with ethynylmagnesium bromide (III) in the presence of CuCl gave 1,4-pentadiyne (Ia). Rearrangement of Ia with KOBut led to 1,3-pentadiyne (IV), while treatment with Br2 furnished 1,2,4,5-tetrabromo-1,4-pentadiene (V). Oxidation of Ia with
描述了一系列含有末端乙炔基(Ia–e)的线性1,4-聚炔的合成和一些反应。在CuCl存在下,炔丙基溴(II)与乙炔基溴化镁(III)反应,得到1,4-戊二炔(Ia)。1a的重排用甲部吨导致1,3- pentadiyne(IV),同时用BR处理2布置1,2,4,5-四溴-1,4-戊二烯(V)。O 2,CuCl和NH 4氧化IaCl产生线性二聚体(VIa)[用KOH重新排列为2,4,6,8-癸二炔(VIII)]和线性三聚体(VIb)。粗氧化产物的氢化得到衍生自VIa,VIb,直链四聚体(VIc)和环状四聚体(VII)的饱和烃,但都不衍生自Ia的环状二聚体或环状三聚体。类似地,在吡啶中用Cu(OAc)2氧化Ia并随后氢化导致衍生自VIa和VIb的饱和烃,但没有一个衍生自环状二聚体或环状三聚体。为了制备环癸烷作为比较化合物,在沸腾的EtOH中用阮内镍处理了衍生自环癸烷的环乙烯二硫缩酮(X),但该反