在不同条件下进行了三种具有不同N,N-二烷基酰胺官能团,N,N-二异丙基酰胺(DiPA),哌啶酰胺(PiA)和顺式-2,6-二甲基哌啶酰胺(DMPA)的1,3-丁二烯衍生物的阴离子聚合并将它们的聚合行为与N,N进行比较先前已报道过二乙酰胺类似物(DEA)。当在-78°C下用钾抗衡离子进行DiPA的聚合时,仅形成痕量的低聚物,而当DiPA在0°C下在LiCl存在下聚合时,以中等收率获得了分子量分布窄的聚合物。 。当在20℃的较高温度下进行聚合时,观察到分子量降低和分子量分布变宽,这大概是由于上限温度的影响。在DMPA的情况下,在0°C时不会形成聚合物,而分子量分布相对较宽的聚合物(M w / M n= 1.2)在20°C下获得。PiA的聚合速率比其他单体的聚合速率快得多,即使在-78°C下24小时仍可以高收率获得聚(PiA)。所得聚合物的微观结构仅对聚(DMPA)为1,4-,而1,2-结构的
α-Allenic ethers 2 are prepared by the reaction of 1,4-dialkoxy-2-butynes 1 with lithium aluminium hydride and magnesium bromide. Tertiary α-allenic amines 4 are obtained by treating 4-dialkylamine-1-methoxy-2-butynes 3 with lithium aluminium hydride and aluminium chloride.
Synthesis and transformations of metallacycles 39. Zr-Catalyzed cyclomagnesiation of N-containing allenes
作者:V. A. D’yakonov、A. A. Makarov、E. Kh. Makarova、T. V. Tyumkina、U. M. Dzhemilev
DOI:10.1007/s11172-012-0022-9
日期:2012.1
Catalytic cyclomagnesiation of N-containing 1,2-dienes with Et2Mg in the presence of the Zr-based complexes affords 2-(aminoalkylidene)magnesacyclopentanes in 68–84% yields.
Synthèse régiosélective d'amines α-alléniques par aminométhylation-désilylation de propargyltriméthylsilanes
作者:D Damour、J Pornet、B Randrianoelina、L Miginiac
DOI:10.1016/0022-328x(90)85470-j
日期:1990.10
Cyclomagnesiation of nitrogen-containing 1,2-dienes with grignard compounds catalyzed by Cp2TiCl2
作者:V. A. D’yakonov、A. A. Makarov、E. Kh. Makarova、L. M. Khalilov、U. M. Dzhemilev
DOI:10.1134/s1070428012030025
日期:2012.3
Cyclomagnesiation of nitrogen-containing 1,2-dienes with Grignard compounds in the presence of activated magnesium and Cp2TiCl2 as catalyst afforded 2,5-bis(aminoalkylidene)magnesacyclopentanes in high yield.
DAMOUR, D.;PORNET, J.;RANDRIANOELINA, B.;MIGINIAC, L., J. ORGANOMET. CHEM., 396,(1990) N-3, C. 289-297
作者:DAMOUR, D.、PORNET, J.、RANDRIANOELINA, B.、MIGINIAC, L.