Separation and NMR studies on lignans of Raulinoa echinata

Abstract

Investigation of the leaves of Raulinoa echinata Cowan (Rutaceae) has led to the isolation of several furofuran (2,6‐diaryl‐3,7‐dioxabicyclo[3.3.0]‐octane) lignan derivatives, namely (+)‐sesamin, (+)‐eudesmin, (+)‐methylpiperitol (= kobusin), (+)‐piperitol‐γ,γ‐dimethylallylether and the corresponding epi compounds: (+)‐asarinin, (+)‐epieudesmin, (+)‐methylxanthoxylol, (+)‐methylpluviatilol, (+)‐xanthoxylol‐γ,γ‐dimethylallylether and (+)‐pluviatilol‐γ,γ‐dimethylallylether. This is the first report of the chromatographic separation of the epimers (+)‐methylxanthoxylol/(+)‐methylpluviatilol and (+)‐xanthoxylol‐γ,γ‐dimethylallylether/(+)‐pluviatilol‐γ,γ‐dimethylallylether and of their NMR nOe difference studies. Copyright © 2001 John Wiley & Sons, Ltd.

Larvicidal activity of lignans and alkaloid identified in Zanthoxylum piperitum bark toward insecticide-susceptible and wild Culex pipiens pallens and Aedes aegypti

“…The active constituents were determined to be the furofuranoid lignans (–)-asarinin (1), (+)-XDA (2) and sesamin (4), and the isobutylamide alkaloid pellitorine (3). The interpretations of the proton and carbon signals of compounds 1, 2, 3, and 4 were largely consistent with those of Perumalsamy et al [22], Biavatti et al [52], Perumalsamy et al [22] and Park et al [44], and Ju et al [53], respectively. XDA was isolated from Z. piperitum as a new larvicidal constituent.…”

Larvicidal activity of lignans and alkaloid identified in Zanthoxylum piperitum bark toward insecticide-susceptible and wild Culex pipiens pallens and Aedes aegypti

“…The active constituents were determined to be the furofuranoid lignans (–)-asarinin (1), (+)-XDA (2) and sesamin (4), and the isobutylamide alkaloid pellitorine (3). The interpretations of the proton and carbon signals of compounds 1, 2, 3, and 4 were largely consistent with those of Perumalsamy et al [22], Biavatti et al [52], Perumalsamy et al [22] and Park et al [44], and Ju et al [53], respectively. XDA was isolated from Z. piperitum as a new larvicidal constituent.…”

Evaluation of Insecticidal Activity of Diterpenes and Lignans from Aristolochia malmeana against Anticarsia gemmatalis

“…138–141 °C ]; [α] D 25 −54.7 ( c 0.3, CHCl 3 ) [lit. +66.0 ( c 0.1, CHCl 3 ) ]; IR data were consistent with those previously reported ; ESI-MS, m / z 371 [M + H] + ; 1 H NMR (500 MHz, CDCl 3 ) δ 6.87 (1H, br s, H-2), 6.79 (2H, br s, H-5, H-6), 3.82 (3H, s, 4-OMe), 3.83 (3H, s, 3-OMe), 4.81 (1H, d, J = 5.5 Hz, H-7), 3.27 (1H, dtd, J = 8.0, 7.0, 5.5 Hz, H-8), 3.25 (1H, t, J = 7.0 Hz, H-9 a ), 3.77 (1H, t, J = 7.0 Hz, H-9 b ), 6.81 (1H, d, J = 1.0 Hz, H-2′), 6.71 (1H, d, J = 8.0 Hz, H-5′), 6.78 (1H, dd, J = 8.0, 1.0 Hz, H-6′), 5.88, 5.89 (2H, 2 × d, w 1/2 = 1.5 Hz, OCH 2 O), 4.37 (1H, d, J = 7.0 Hz, H-7′), 2.82 (1H, dddd, J = 8.0, 7.0, 6.5, 1.0 Hz, H-8′), 3.79 (1H, dd, J = 9.5, 6.5 Hz, H-9 a ′), 4.06 (1H, dd, J = 9.5, 1.0 Hz, H-9 b ′); 13 C NMR (126 MHz, CDCl 3 ) δ 130.9 (C-1), 108.9 (C-2), 148.8 (C-3), 148.0 (C-4), 111.0 (C-5), 117.6 (C-6), 55.8 (2 × OMe), 82.0 (C-7), 50.1 (C-8), 69.7 (C-9), 135.1 (C-1′), 106.5 (C-2′), 147.9 (C-3′), 147.1 (C-4′), 108.1 (C-5′), 119.5 (C-6′), 101.0 (OCH 2 O), 87.6 (C-7′), 54.5 (C-8′), 70.9 (C-9′).…”

Calmodulin Inhibitors from Leucophyllum ambiguum

“…In addition, a new singlet appearing at δ H 4.00 due to an extra methoxyl group was observed in the 1 H NMR spectrum; this methoxyl group signal showed a NOESY correlation with the resonance at δ H 5.92 (OCH 2 O), thus indicating attachment of the third methoxyl at C-2‘. The diequatorial orientation of the aromatic rings was supported by the chemical shifts of C-1/C-1‘, H-1/H-5, and H-2/H-6. − The cis arrangement of the fused tetrahydrofurofuran rings in all natural lignans restricts the configurations of the bridge atoms C-1 and C-5 to be either ( R )/( R ) or ( S )/( S ) . According to literature data, all (+)-sesamin and (+)-kobusin type of lignans have the absolute configuration R at the bridge carbons C-1 and C-5. , In the present work, the novel lignans showed positive optical rotations implying the C-5 ( R )/C-1 ( R ) absolute configuration.…”

Larvicidal activity of lignans and alkaloid identified in Zanthoxylum piperitum bark toward insecticide-susceptible and wild Culex pipiens pallens and Aedes aegypti

“…The active constituents were determined to be the furofuranoid lignans (–)-asarinin (1), (+)-XDA (2) and sesamin (4), and the isobutylamide alkaloid pellitorine (3). The interpretations of the proton and carbon signals of compounds 1, 2, 3, and 4 were largely consistent with those of Perumalsamy et al [22], Biavatti et al [52], Perumalsamy et al [22] and Park et al [44], and Ju et al [53], respectively. XDA was isolated from Z. piperitum as a new larvicidal constituent.…”

Evaluation of Insecticidal Activity of Diterpenes and Lignans from Aristolochia malmeana against Anticarsia gemmatalis

“…138–141 °C ]; [α] D 25 −54.7 ( c 0.3, CHCl 3 ) [lit. +66.0 ( c 0.1, CHCl 3 ) ]; IR data were consistent with those previously reported ; ESI-MS, m / z 371 [M + H] + ; 1 H NMR (500 MHz, CDCl 3 ) δ 6.87 (1H, br s, H-2), 6.79 (2H, br s, H-5, H-6), 3.82 (3H, s, 4-OMe), 3.83 (3H, s, 3-OMe), 4.81 (1H, d, J = 5.5 Hz, H-7), 3.27 (1H, dtd, J = 8.0, 7.0, 5.5 Hz, H-8), 3.25 (1H, t, J = 7.0 Hz, H-9 a ), 3.77 (1H, t, J = 7.0 Hz, H-9 b ), 6.81 (1H, d, J = 1.0 Hz, H-2′), 6.71 (1H, d, J = 8.0 Hz, H-5′), 6.78 (1H, dd, J = 8.0, 1.0 Hz, H-6′), 5.88, 5.89 (2H, 2 × d, w 1/2 = 1.5 Hz, OCH 2 O), 4.37 (1H, d, J = 7.0 Hz, H-7′), 2.82 (1H, dddd, J = 8.0, 7.0, 6.5, 1.0 Hz, H-8′), 3.79 (1H, dd, J = 9.5, 6.5 Hz, H-9 a ′), 4.06 (1H, dd, J = 9.5, 1.0 Hz, H-9 b ′); 13 C NMR (126 MHz, CDCl 3 ) δ 130.9 (C-1), 108.9 (C-2), 148.8 (C-3), 148.0 (C-4), 111.0 (C-5), 117.6 (C-6), 55.8 (2 × OMe), 82.0 (C-7), 50.1 (C-8), 69.7 (C-9), 135.1 (C-1′), 106.5 (C-2′), 147.9 (C-3′), 147.1 (C-4′), 108.1 (C-5′), 119.5 (C-6′), 101.0 (OCH 2 O), 87.6 (C-7′), 54.5 (C-8′), 70.9 (C-9′).…”

Calmodulin Inhibitors from Leucophyllum ambiguum

“…In addition, a new singlet appearing at δ H 4.00 due to an extra methoxyl group was observed in the 1 H NMR spectrum; this methoxyl group signal showed a NOESY correlation with the resonance at δ H 5.92 (OCH 2 O), thus indicating attachment of the third methoxyl at C-2‘. The diequatorial orientation of the aromatic rings was supported by the chemical shifts of C-1/C-1‘, H-1/H-5, and H-2/H-6. − The cis arrangement of the fused tetrahydrofurofuran rings in all natural lignans restricts the configurations of the bridge atoms C-1 and C-5 to be either ( R )/( R ) or ( S )/( S ) . According to literature data, all (+)-sesamin and (+)-kobusin type of lignans have the absolute configuration R at the bridge carbons C-1 and C-5. , In the present work, the novel lignans showed positive optical rotations implying the C-5 ( R )/C-1 ( R ) absolute configuration.…”

Larvicidal activity of lignans and alkaloid identified in Zanthoxylum piperitum bark toward insecticide-susceptible and wild Culex pipiens pallens and Aedes aegypti

“…The active constituents were determined to be the furofuranoid lignans (–)-asarinin (1), (+)-XDA (2) and sesamin (4), and the isobutylamide alkaloid pellitorine (3). The interpretations of the proton and carbon signals of compounds 1, 2, 3, and 4 were largely consistent with those of Perumalsamy et al [22], Biavatti et al [52], Perumalsamy et al [22] and Park et al [44], and Ju et al [53], respectively. XDA was isolated from Z. piperitum as a new larvicidal constituent.…”

Evaluation of Insecticidal Activity of Diterpenes and Lignans from Aristolochia malmeana against Anticarsia gemmatalis

“…138–141 °C ]; [α] D 25 −54.7 ( c 0.3, CHCl 3 ) [lit. +66.0 ( c 0.1, CHCl 3 ) ]; IR data were consistent with those previously reported ; ESI-MS, m / z 371 [M + H] + ; 1 H NMR (500 MHz, CDCl 3 ) δ 6.87 (1H, br s, H-2), 6.79 (2H, br s, H-5, H-6), 3.82 (3H, s, 4-OMe), 3.83 (3H, s, 3-OMe), 4.81 (1H, d, J = 5.5 Hz, H-7), 3.27 (1H, dtd, J = 8.0, 7.0, 5.5 Hz, H-8), 3.25 (1H, t, J = 7.0 Hz, H-9 a ), 3.77 (1H, t, J = 7.0 Hz, H-9 b ), 6.81 (1H, d, J = 1.0 Hz, H-2′), 6.71 (1H, d, J = 8.0 Hz, H-5′), 6.78 (1H, dd, J = 8.0, 1.0 Hz, H-6′), 5.88, 5.89 (2H, 2 × d, w 1/2 = 1.5 Hz, OCH 2 O), 4.37 (1H, d, J = 7.0 Hz, H-7′), 2.82 (1H, dddd, J = 8.0, 7.0, 6.5, 1.0 Hz, H-8′), 3.79 (1H, dd, J = 9.5, 6.5 Hz, H-9 a ′), 4.06 (1H, dd, J = 9.5, 1.0 Hz, H-9 b ′); 13 C NMR (126 MHz, CDCl 3 ) δ 130.9 (C-1), 108.9 (C-2), 148.8 (C-3), 148.0 (C-4), 111.0 (C-5), 117.6 (C-6), 55.8 (2 × OMe), 82.0 (C-7), 50.1 (C-8), 69.7 (C-9), 135.1 (C-1′), 106.5 (C-2′), 147.9 (C-3′), 147.1 (C-4′), 108.1 (C-5′), 119.5 (C-6′), 101.0 (OCH 2 O), 87.6 (C-7′), 54.5 (C-8′), 70.9 (C-9′).…”

Calmodulin Inhibitors from Leucophyllum ambiguum

“…In addition, a new singlet appearing at δ H 4.00 due to an extra methoxyl group was observed in the 1 H NMR spectrum; this methoxyl group signal showed a NOESY correlation with the resonance at δ H 5.92 (OCH 2 O), thus indicating attachment of the third methoxyl at C-2‘. The diequatorial orientation of the aromatic rings was supported by the chemical shifts of C-1/C-1‘, H-1/H-5, and H-2/H-6. − The cis arrangement of the fused tetrahydrofurofuran rings in all natural lignans restricts the configurations of the bridge atoms C-1 and C-5 to be either ( R )/( R ) or ( S )/( S ) . According to literature data, all (+)-sesamin and (+)-kobusin type of lignans have the absolute configuration R at the bridge carbons C-1 and C-5. , In the present work, the novel lignans showed positive optical rotations implying the C-5 ( R )/C-1 ( R ) absolute configuration.…”