Syntheses of Tertiary Tetraamines and Quaternary Pentaamines with Three and Four Methylene Chain Units.
作者:Masaru NIITSU、Hirao SANO、Keijiro SAMEJIMA
DOI:10.1248/cpb.40.2958
日期:——
Tertiary tetraamines and quaternary pentaamines composed of aminopropyl and/or aminobutyl groups were synthesized as authentic samples for the identification of naturally occurring branched polyamines. Four tertiary tetraamines were obtained by alkylating the free secondary amine group of diphthaloyl derivatives of sym-norspermidine or sym-homospermidine with N-(3-bromopropyl)phthalimide or N-(4-bromobutyl)phthalimide in the presence of KF-Celite. Five quaternary pentaamines were obtained by fusing triphthaloyl derivatives of the tertiary tetraamines with an excess amount of N-(3-iodopropyl)phthalimide or N-(4-iodobutyl)phthalimide. The present methods are simple and achieved high yields. The 13C-NMR spectra of these branched polyamines were recorded in D2O as fully protonated forms, and all 13C chemical shifts were assigned consistently.
合成了由氨基丙基和/或氨基丁基组成的叔四胺和季五胺,作为鉴定天然支链多胺的真实样品。在 KF-Celite 的存在下,用 N-(3-溴丙基)邻苯二甲酰亚胺或 N-(4-溴丁基)邻苯二甲酰亚胺烷基化 sym-norspermidine 或 sym-homospermidine 的二邻苯二甲酰衍生物的游离仲胺基团,获得了四种三级四胺。通过将三级四胺的三酞酰基衍生物与过量的 N-(3-碘丙基)邻苯二甲酰亚胺或 N-(4-碘丁基)邻苯二甲酰亚胺融合,得到了五种季戊四胺。本方法简单,产率高。这些支化多胺的 13C-NMR 光谱是在 D2O 中以完全质子化的形式记录的,所有 13C 化学位移的分配都是一致的。