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箭毒蛙中的生物碱:3-丁基-5-丙基吲哚里西啶的两种ω-羟基同系物的结构以及2,5-二取代吡咯烷和2,6-二取代哌啶的存在情况

Alkaloids from dendrobatid frogs: structures of two omega-hydroxy congeners of 3-butyl-5-propylindolizidine and occurrence of 2,5-disubstituted pyrrolidines and a 2,6-disubstituted piperidine.

作者信息

Daly J W, Spande T F, Whittaker N, Highet R J, Feigl D, Nishimori N, Tokuyama T, Myers C W

出版信息

J Nat Prod. 1986 Mar-Apr;49(2):265-80. doi: 10.1021/np50044a012.

DOI:10.1021/np50044a012
PMID:3734811
Abstract

Forty alkaloids were detected and characterized from skin extracts of high- and low-elevation populations of the poison frog Dendrobates histrionicus from northwestern Colombia. Combined gc/ms with NH3 or ND3 in a chemical ionization mode detected protonated parent ions and determined the number of exchangeable NH and OH hydrogens. Six previously unknown dendrobatid alkaloids were characterized. Two were 2,5-disubstituted pyrrolidines, which included pyrrolidine 197B, a trans-2-butyl-5-pentylpyrrolidine, while a third was a 2,6-dipentylpiperidine. Indolizidines 239AB and 239CD had the same relative configuration as the parent alkaloid 223AB [(5E,9E)3-butyl-5-propylindolizidine] and contained, respectively, a omega-hydroxy group in the propyl or butyl side chain. The profiles of alkaloids in the new northern populations of D. histrionicus are typical of the species in containing a set of about eight histrionicotoxins, in marked contrast to a related species, Dendrobates lehmanni, which does not contain histrionicotoxins.

摘要

从哥伦比亚西北部高地和低地的箭毒蛙(Dendrobates histrionicus)皮肤提取物中检测并鉴定出了40种生物碱。气相色谱/质谱联用技术结合氨气或重氢氨,以化学电离模式检测到质子化母离子,并确定了可交换的NH和OH氢原子的数量。鉴定出了6种此前未知的箭毒蛙生物碱。其中两种是2,5 - 二取代吡咯烷,包括吡咯烷197B,即反式 - 2 - 丁基 - 5 - 戊基吡咯烷,第三种是2,6 - 二戊基哌啶。吲哚里西定239AB和239CD与母体生物碱223AB [(5E,9E)-3 - 丁基 - 5 - 丙基吲哚里西定]具有相同的相对构型,且分别在丙基或丁基侧链中含有一个ω - 羟基。新发现的北方种群的D. histrionicus生物碱谱具有该物种典型特征,即含有一组约8种组织胺毒素,这与相关物种Dendrobates lehmanni形成鲜明对比,后者不含组织胺毒素。

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