7a-O-methyldeguelol, a modified rotenoid with an open ring-C, from the roots of Derris trifoliata

doi:10.1016/j.phytochem.2005.02.005

Phytochemistry

Volume 66, Issue 6, March 2005, Pages 653-657

https://doi.org/10.1016/j.phytochem.2005.02.005 Get rights and content

Abstract

From the acetone extract of the roots of Derris trifoliata an isoflavonoid derivative, named 7a-O-methyldeguelol, a modified rotenoid with an open ring-C, representing a new sub-class of isoflavonoids (the sub-class is here named as rotenoloid), was isolated and characterised. In addition, the known rotenoids, rotenone, deguelin and α-toxicarol, were identified. The structures were determined on the basis of spectroscopic evidence. Rotenone and deguelin were identified as the larvicidal principles of the acetone extract of the roots of Derris trifoliata.

Graphical abstract

From the roots of Derris trifoliata an isoflavonoid derivative (1), a modified rotenoid with an open ring-C, representing a new sub-class of isoflavonoids (the sub-class named rotenoloid) was isolated and characterised. The structure was determined on the basis of spectroscopic evidence.

Introduction

In our interest on the identification of larvicidal compounds from plants, we have reported the larvicidal activities of rotenoids isolated from the seeds of Millettia dura Dunn (Yenesew et al., 2003). Rotenoids also occur in the genera Derris, Lonchocarpus and Tephrosia of the family Leguminosae (Dewick, 1994). Some species belonging to these genera including Derris elliptica, are commercially cultivated as a source of insecticidal rotenoids (Fukami and Nakajima, 1971).

The genus Derris is represented in Kenya by Derris trifoliata Lour. Recent investigation of the stems of D. trifoliata has resulted in the identification of rotenoids with cancer chemopreventive properties (Ito et al., 2004). From the roots of this plant we report here the isolation and characterization of a novel isoflavonoid derivative (1) representing a new sub-class of isoflavonoids.

Section snippets

Results and discussion

The acetone extract of the roots of Derris trifoliata showed high toxicity against the second instar larvae of the mosquito Culex quinquefasciatus with LC₅₀ value of 1.35 ± 0.7 μg/ml. From this extract, by the use of a combination of chromatographic methods, a novel isoflavonoid derivative (1) along with three known compounds was isolated. The known compounds were identified as the rotenoids, (−)-rotenone (2), (−)-deguelin (3) and (−)-α-toxicarol (4), by comparison of their spectroscopic data with

General

Analytical TLC: Merck pre-coated silica gel 60 F₂₅₄ plates. CC on oxalic acid impregnated silica gel 60 (70–230 mesh). EIMS: direct inlet, 70 eV, on a SSQ 710, Finnigan MAT mass spectrometer. ¹H and ¹³C NMR on Bruker or Varian-Mercury spectrometers using TMS as int. standard. HMQC and HMBC spectra were acquired using the standard Bruker software.

Plant material

The roots of Derris trifoliata Lour were collected in Coast Province, Kenya, in August 2003. The plant was identified at the University Herbarium,

Acknowledgements

We acknowledge the financial support by African Institute for Capacity Development (AICAD), the Deutsche Forschungsgemeinschaft, Germany, Grant No. Pe 264/14-5 and the Bundesministerium für Zusammenarbeit, Grant No. Pe 264/14-6. Mr S. G. Mathenge is thanked for identification of the plant material. A.Y. is grateful to the German Academic Exchange Service (DAAD) for a three month research visit to the University of Potsdam.

References (12)

C.M. Cerda-Garcia-Rojas et al.
A PC program for calculation of dihedral angles from ¹H NMR data
Tetrahedron Computer Methodology
(1990)
E. Dagne et al.
Flavonoids and isoflavonoids from Tephrosia fulvinervis and Tephrosia pentaphylla
Phytochemistry
(1989)
A. Yenesew et al.
Two prenylated flavanones from stem bark of Erythrina burttii
Phytochemistry
(1998)
P.M. Dewick
Isoflavonoids
M.J. Frisch et al.
Gaussian 98, Revision A.11.3
(2002)
H. Fukami et al.
Rotenone and rotenoids

There are more references available in the full text version of this article.

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Rotenoids, 7a-O-methylelliptonol, as an insecticide, vertebrate poison, and acaricide was isolated from the stem extracts of D. trifoliata. Flavanone, 4′,5,7-trihydroxy-6,8-di-(2-hydroxy-3-methylbut-3-enyl)-flavanone, was isolated from the aerial parts of D. trifoliata, together with eleven known compounds; rotenone, tephrosin, 12a-hydroxyrotenone, deguelin, 6a,12a-dehydrorotenone, dehydrodeguelin, 7a-O-methyldeguelol, 7a-O-methylelliptonol, 5,7,3′,4′-tetrahydroxy-6,8-diprenylisoflavone, daidzein and 4′-hydroxy-7-methoxyflavanone.2′, 4′-dihydroxy-4-methoxy-3′-prenyl chalcone and leutolin [10–12]. Sonneratia alba, a true mangrove are used as traditional medicine for swellings and sprains, it has many commercial applications.
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Phytochemistry

Abstract

Graphical abstract

Introduction

Section snippets

Results and discussion

General

Plant material

Acknowledgements

References (12)

A PC program for calculation of dihedral angles from ¹H NMR data

Tetrahedron Computer Methodology

Flavonoids and isoflavonoids from Tephrosia fulvinervis and Tephrosia pentaphylla

Phytochemistry

Two prenylated flavanones from stem bark of Erythrina burttii

Phytochemistry

Isoflavonoids

Gaussian 98, Revision A.11.3

Rotenone and rotenoids

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Two unusual rotenoid derivatives, 7a-O-methyl-12a-hydroxydeguelol and spiro-13-homo-13-oxaelliptone, from the seeds of Derris trifoliata

Substituted tubaic acids, new oxidative rotenoid metabolites from Lonchocarpus nicou

<sup>1</sup>H NMR Handbook of Natural Products: Flavones, Quinones, Phenylpropanoids, and Stilbenes