某些含有机胂二茂铁基胺衍生物的合成

Syntheses of Organoarsino-Containing Ferrocenyl Amine Derivatives

锂化二甲氨甲基二茂铁与二本基氯化胂反应生成2-(二苯胂基)二甲氨甲基二茂铁及很少量的2,5-二(二苯胂基)二甲氨甲基二茂铁.在四甲基乙二胺(TMEDA)存在下,锂化的二甲氨甲基二茂铁与二苯基氯化胂反应则得到2,1’-二(二苯胂基)二甲氨甲基二茂铁.在不同条件下上述产物与过量碘甲烷作用生成多种不同的甲碘化物.

N,N-dimethylaminomethylferrocene ( Ⅰ ) was lithiated to the monolithio compound, which was then reacted with an equimolar diphenylchloroarsine (DPCA) to form 2-(dtpheny-larsino) dimethylaminomethylferrocene ( Ⅱ ) and a small amount of 2, 5-di (diphenylarsino) dimethylamino-methylferrocene ( Ⅲ ) as the by-product. When I was lithiated in the presence of N,N,N' ,N' -tetramethyl ethylene diamine (TMEDA) and then condensed with 2 mol of DPCA, 2,1' -di(diphenylarsino)dimethylaminomethylferrocene (Ⅳ) was obtained. When the products were allowed to react with an excess of methyl iodide, different methiodides were formed under different conditions. At 40℃ and a reaction time of 10 min, Ⅱ yielded a monomethiodide Ⅴ , which on hydrolysis with aqueous alkali yielded 2-(diphenylarsino)ferrocenylmethanol ( Ⅵ ). This shows that Ⅴ is a quaternary ammonium salt instead of an arsonium one, otherwise it would yield Ⅰ as the hydrolyzed product. When the reaction time was prolonged to 9 h, Ⅰ gave a dimethiodide Ⅶ, which should be a quaternary ammonium-arsonium compound. When IV was allowed to react with an excess of methyl iodide at 80℃ for 11 h, a trimethiodide of quaternary ammonium-diarsonium compound Ⅷ was produced. The structures of the products were confirmed by elemental analysis, IR and 1H NMR spectra. The MS of Ⅱ and Ⅲare also given.