Reactions of amines and active methylene compounds with buta-1,3-diene and isoprene: catalysis by nickel, cobalt, rhodium, and iridium complexes
作者:Raymond Baker、Alan Onions、Roger J. Popplestone、Trevor N. Smith
DOI:10.1039/p29750001133
日期:——
amounts of hydrochloric acid. Some reactions of diethylamine, pyrrolidine, and aniline have been studied. Reaction of benzyl methyl ketone and diethyl malonate with buta-1,3-diene catalysed by NiCl2–Ph3P–NaBH4 yields mainly the 2 : 1 adducts. With the system CoCI2-Ph3P-NaBH4, prior formation of the sodium salt of diethyl malonate was required for reaction with buta-1,3-diene.
在NiCl 2 -Ph 3 P-NaBH 4,CoCl 2 -Ph 3 P-NaBH 4 -AI(OPr i)3和-存在下,buta -1,3-二烯与吗啉和二正丙胺的反应已显示IrCl 3可以产生两种异构体2:1和1:1加合物,前者占主导地位。在存在RhCI 3和CoCI 2 –Ph 3 P–NaBH 4的情况下,主要得到了1:1的加合物。当配体二异丙氧基苯基膦,三(邻甲苯基)亚磷酸酯和三((尽管发现与最后一个配体仅形成2∶1的加合物,但是使用了亚磷酸邻-联苯基基)。向RhCl 3催化剂中添加三苯基膦和-ar基也有利于形成2:1加合物,并且少量的盐酸显着提高了IrCl 3的催化活性。已经研究了二乙胺,吡咯烷和苯胺的一些反应。NiCl 2 -Ph 3 P-NaBH 4催化苄基甲基酮和丙二酸二乙酯与1,3-丁二烯的反应,主要生成2:1的加合物。通过系统CoCI 2 -Ph 3 P-NaBH 4,需要先形成丙二酸二乙酯的钠盐才能与1