Dehydropyrrolizidine Alkaloids in Two Cryptantha Species: Including Two New Open Chain Diesters One of Which is Amphoteric
Article first published online: 15 OCT 2012
Published 2012. This article is a US Government work and is in the public domain in the USA.
Volume 24, Issue 3, pages 201–212, May/June 2013
How to Cite
Colegate, S. M., Gardner, D. R., Davis, T. Z., Betz, J. M. and Panter, K. E. (2013), Dehydropyrrolizidine Alkaloids in Two Cryptantha Species: Including Two New Open Chain Diesters One of Which is Amphoteric. Phytochem. Anal., 24: 201–212. doi: 10.1002/pca.2400
- Issue published online: 16 APR 2013
- Article first published online: 15 OCT 2012
- Manuscript Revised: 13 AUG 2012
- Manuscript Accepted: 13 AUG 2012
- Manuscript Received: 4 JUL 2012
- HPLC–MS: amphoteric pyrrolizidine alkaloid;
- dehydropyrrolizidine alkaloids;
- winged cryptantha;
- Cryptantha inequata;
- Cryptantha utahensis;
- scented catseye
A livestock poisoning outbreak near Kingman, Arizona, USA, potentially linked to dehydropyrrolizidine alkaloids, prompted an evaluation of some local plants for the presence of these hepatotoxic alkaloids.
To qualitatively and quantitatively examine two species of Cryptantha, a Boraginaceous genus previously shown to produce potentially toxic pyrrolizidine alkaloids, collected from the vicinity of Kingman, Arizona.
Plant extracts were analysed using HPLC–electrospray ionisation (+)–MS and MS/MS to determine the presence of dehydropyrrolizidine alkaloid esters. Identities were confirmed by comparison of chromatographic and MS data with authenticated standards and, in the case of the previously undescribed alkaloids, using one- and two-dimensional NMR spectroscopy and high-resolution mass measurement.
Cryptantha inequata and C. utahensis were shown to produce retronecine-based dehydropyrrolizidine alkaloids at approximately 0.05% and 0.09% w/w respectively. Cryptantha inequata produced mainly echimidine, acetylechimidine and echiuplatine; dehydropyrrolizidine alkaloids that were previously associated with Echium plantagineum. The previously undescribed structure of echiuplatine was elucidated as an amphoteric, open chain diester with angelic acid and 3-hydroxy-3-methylglutaric acid. Along with lycopsamine, intermedine and dihydroxyechiumine, C. utahensis produced cryptanthine, a previously undescribed open chain diester alkaloid esterified with angelic acid and 2,3-dihydroxy-2-methylbutanoic acid. All pyrrolizidine alkaloids detected were present in the plants mainly as their N-oxides.
The retronecine-based alkaloids detected in both Cryptantha species herein investigated aligns them within the Krynitzkia subgenus. The dehydropyrrolizidine alkaloids detected are expected to be toxic but the low levels in the plants potentially mitigate the risk. The identification of the amphoteric echiuplatine provides a cautionary note with respect to the analysis of total dehydropyrrolizidine alkaloid content. Published 2012. This article is a US Government work and is in the public domain in the USA.