Mass spactra of diterpene alkaloids with the lycoctonine skeleton

Yunusov, M. S.; Rashkes, Ya. V.; Tel'nov, V. A.; Yunusov, S. Yu.

doi:10.1007/bf00568584

Cited by 8 publications

(12 citation statements)

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“…Therefore, the methoxyls were located on C-1, C-6, C-16, and C-18. The appearance of a strong peak for [M -31] + in the mass spectrum of 1 confirmed that a methoxyl was located on C-1 [2].…”

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confidence: 60%

Karaconitine, a new C19-norditerpenoid alkaloid from Aconitum karakolicum roots

Usmanova

Aisa

2011

Chem Nat Compd

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547.944/945The known alkaloids aconitine, benzoylaconine, and songorine and the new C 19 -norditerpenoid alkaloid karaconitine were isolated from roots of Aconitum karakolicum Rapaics (Ranunculaceae). The structure of karaconitine was established using ESI-mass spectra, 1D ( 1 H and 13 C) and 2D NMR (HSQC, HMBC) and DEPT spectral data, and comparison of its 13 C NMR spectrum with that of aconine.In continuation of research on the alkaloid composition of roots of Aconitum karakolicum Rapaics (Ranunculaceae), we isolated in addition to the known alkaloids aconitine, benzoylaconine, and songorine [1] a new base 1 of formula C 24 H 39 NO 9 with mp 155-157°C that we called karaconitine.The mass spectrum of 1 showed peaks for ions with m/z 485 [M] + , 470 [M -15] + , and 454 [M -31] + .The proton spectrum had resonances for N-methyl, four methoxyls, and protons geminal to three hydroxyls. Its DEPT spectrum gave resonances for 24 C atoms including 4 singlets, 11 doublets, 4 triplets, and 5 quartets , and 16-OCH 3 . The chemical shifts (CSs) of C-13, C-14, and C-15 suggested that hydroxyls were located in these positions. Resonances of C-14 and C-15 in the HSQC spectrum showed cross peaks with resonances for H-14 (3.93, d, 1H, J = 5.2) and H-15 (4.77, d, 1H, J = 6.0). The CSs, multiplicity, and SSCC of resonances for H-14 and H-15 were due to the presence of D-oriented OH groups on C-14 and C-15. These results were consistent with hydroxyls on C-13, C-14, and C-15. The presence of an OH group on C-13 caused a weak-field shift of the resonance for C-12 to the region 33.5-38.0 ppm [3]. The resonance for C-12 was observed in the 13 C NMR spectrum at 36.23 ppm and confirmed that C-13 had an OH group.The DEPT spectrum of 1 showed a singlet for the C atom at 76.02 ppm. The CS of this resonance indicated that C-8 contained a tertiary OH group. The resonance for C-8 was observed in the region G 75.5-76.5 ppm with simultaneous occurrence of an D-oriented hydroxyl on C-15 [3]. Therefore, C-8 was substituted with a hydroxyl.

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confidence: 60%

Karaconitine, a new C19-norditerpenoid alkaloid from Aconitum karakolicum roots

Usmanova

Aisa

2011

Chem Nat Compd

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“…The base peak in the mass spectrum of 1 ([M -31] + ) indicated that there was a 1-methoxy group [2]. A broad singlet at 3.88 ppm in the PMR of 1 was consistent with the presence of a C-6 β-methoxyl [3]; three 3H triplets at 0.91, 1.07, and 1.17 ppm, three ethyl groups.…”

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confidence: 94%

“…Delphinium alpinum E. D. Khairitdinova, 1 E. M. Tsyrlina, 1 L. V. Spirikhin, 1 UDC 547.944/945 N. I. Fedorov, 2 …”

Section: Alpinine a New Norditerpene Alkaloid Frommentioning

confidence: 99%

Alpinine, A New Norditerpene Alkaloid from Delphinium alpinum

et al. 2005

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“…The high-resolution mass spectrum gave molecular weight 465.2715 for 1, which corresponded to the empirical formula C 25 H 39 NO 7 . The fact that the peak for the ion [M -17] + was the base peak suggested that C-1 had an OH group [4]. Peaks for ions [M -56] + and [M -87] + also suggested that there was a hydroxyl in the 1-position and a methoxyl in the 18-position [5,6].…”

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confidence: 96%

Uraphine, a new norditerpene alkaloid from the aerial part of Delphinium uralense

et al. 2008

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The new norditerpene alkaloid uraphine, for which the structure 1α, 6β-dihydroxy-7,8-methylenedioxy-14α,16β,18β-trimethoxy-N-ethylaconitane was proposed based on PMR, 13 C NMR, IR, and mass spectral data, was isolated from the aerial part of Delphinium uralense N. The known alkaloids dehydrodelcorine, delpheline, deltaline, deltamine, elasine, deacetylelasine, gigactonine, and lycoctonine were also isolated from the total alkaloids.The plant Delphinium uralense Nevski has a limited distribution and belongs to the complex D. aggr. dictyocarpum DC. (section Delphinastrum DC) [1]. We reported previously on the isolation from the aerial part of this plant collected during the start of budding in the Southern Urals (Zilair Plateau) of methyllycaconitine, delcorine, and grandiflorine (uraline) [2].In continuation of research on the alkaloid composition of the aerial part of D. uralense, we isolated from the benzene extract of the moderately basic fraction (A, pH 6) [2] by column chromatography and semi-preparative HPLC the known alkaloids dehydrodelcorine, delpheline, deltaline, deltamine, and elasine, and alkaloid 1, which has not previously been described and which we called uraphine. We also isolated deacetylelasine, which was isolated by us for the first time from plant material and has been prepared previously via alkaline hydrolysis of elasine [3]. We isolated the known alkaloids gigactonine and lycoctonine from the strongly basic fraction (B, pH 12).According to IR spectroscopy, 1 contained hydroxyls (3300-3500 cm −1 ). The high-resolution mass spectrum gave molecular weight 465.2715 for 1, which corresponded to the empirical formula C 25 H 39 NO 7 . The fact that the peak for the ion [M -17] + was the base peak suggested that C-1 had an OH group [4]. Peaks for ions [M -56] + and [M -87] + also suggested that there was a hydroxyl in the 1-position and a methoxyl in the 18-position [5,6]. The location of one of the three methoxyls in the C-18 position was confirmed by the presencee in the 13 C NMR of 1 of a triplet at δ 78.5 ppm. The presence in the PMR of 1 of a 1H singlet for H-6α at δ 4.37 ppm placed a β-OH group on C-6 [7]. Furthermore, a 1H triplet (J = 4.5 Hz) was observed at δ 3.71 ppm, indicating that C-14 contained an α-methoxyl [8].

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Mass spactra of diterpene alkaloids with the lycoctonine skeleton

Cited by 8 publications

References 1 publication

Karaconitine, a new C19-norditerpenoid alkaloid from Aconitum karakolicum roots

Karaconitine, a new C19-norditerpenoid alkaloid from Aconitum karakolicum roots

Alpinine, A New Norditerpene Alkaloid from Delphinium alpinum

Uraphine, a new norditerpene alkaloid from the aerial part of Delphinium uralense

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