New limonoids from Hortia oreadica and unexpected coumarin from H. superba using chromatography over cleaning Sephadex with sodium hypochlorite

• Published in: Molecules (Basel, Switzerland) Vol. 19; no. 8; pp. 12031 - 12047
• Main Authors: Severino, Vanessa G P, de Freitas, Sâmya D L, Braga, Patrícia A C, Forim, Moacir Rossi, das G F da Silva, M Fátima, Fernandes, João B, Vieira, Paulo C, Venâncio, Tiago
• Format: Journal Article
• Language: English
• Published: Switzerland MDPI AG 12.08.2014; MDPI
• Subjects: Acids; alkaloids; chlorination; Chlorine; Chromatography; coumarins; Coumarins - chemistry; Coumarins - isolation & purification; dihydrocinnamic acids; Fourier transforms; H. brasiliana; H. superba; Hortia oreadica; Limonins - chemistry; Limonins - isolation & purification; limonoids; Natural products; NMR; Nuclear magnetic resonance; Plant Extracts - chemistry; Rutaceae; Rutaceae - chemistry; Scanning electron microscopy; Sephadex LH-20; Sodium Hypochlorite - chemistry; Brazil
• ISSN: 1420-3049; 1420-3049
• DOI: 10.3390/molecules190812031

Previous investigations of H. oreadica reported the presence of a wide spectrum of complex limonoids and dihydrocinnamic acids. Our interest in the Rutaceae motivated a reinvestigation of H. oreadica, H. brasiliana and H. superba searching for other secondary metabolites present in substantial amounts for taxonomic analysis. In a continuation of the investigation of the H. oreadica, three new limonoids have now been isolated 9α-hydroxyhortiolide A, 11β-hydroxyhortiolide C and 1(S*)-acetoxy-7(R*)-hydroxy-7-deoxoinchangin. All the isolated compounds from the Hortia species reinforce its position in the Rutaceae. With regard to limonoids the genus produces highly specialized compounds, whose structural variations do not occur in any other member of the Rutaceae, thus, it is evident from limonoid data that Hortia takes an isolated position within the family. In addition, H. superba afforded the unexpected coumarin 5-chloro-8-methoxy-psoralen, which may not be a genuine natural product. Solid-state cross-polarisation/magic-angle-spinning 13C nuclear magnetic resonance, X-Ray fluorescence and Field-emission gun scanning electron microscopy experiments show that the Sephadex LH-20 was modified after treatment with NaOCl, suggesting that when xanthotoxin (8-methoxy-psoralen) was extracted from cleaning of the gel column, chlorination of the aromatic system occurred.