Transformation of Aconitine to an Isomer of Hypaconitine

Gilman, Robert E.; Marion, Léo

doi:10.1139/v62-259

Cited by 9 publications

(5 citation statements)

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“…Consequently, the remaining lowfield singlet at 76.7 ppm in 13 can be assigned to C-13. The fact that the resonance at 72.8 ppm disappears after pyrolysis of delphinine (5) to the pyro compound (7), and hydrolysis of the latter to 8, supports these assignments. The C-8 and C-13 resonances assigned by Jones2 are not the only ones in 13 which should be corrected.…”

Section: Introductionmentioning

confidence: 62%

“…Delocalization of the free electron pair of the nitrogen will build up a negative charge on C-15, Figure 3. NMR spectra of pyrodelphinine (7) in the region between 4 and 8 ppm ( ) with tetramethylsilane as internal standard. Curves A, B, C, D, E, G, H all in CDCI3.…”

Section: Discussion and Applicationmentioning

confidence: 99%

“…The narrow range (±0.3 ppm) of chemical shifts exhibited by methoxyl carbons of 56.0 ppm in aconitine (1-4) and delphinine-type bases (5, 6, 8, 9, 13-15) suggests assignment to the C-l methoxyl. The methyl resonance at 59.1 ± 0.2 ppm in aconitine-type (1)(2)(3)(4), delphinine-type (5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15), and neoline-type (16)(17)(18)(19)(20)(21)(22)(23)(24)(25)(26)(27) bases and the absence of this resonance in bases A and B examined by Jones2 (where C-l8 is a methyl at 27.4 ppm) suggest the assignment of this resonance to C-l8'. A C-6 methoxyl group is common to aconitine (1-4), delphinine (5-8, 10-13, 15), and neoline-type bases (16)(17)(18)(19)(20)(21)(22)(23)(24)(25), except for condelphine (26) and isotalatizidine (27), and the methyl resonance at 57.9 ± 0.3 may be assigned to this carbon.…”

Section: Introductionmentioning

confidence: 99%

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Carbon-13 nuclear magnetic resonance: aconitine-type diterpenoid alkaloids from Aconitum and Delphinium species

Pelletier¹,

Ďjarmati²

1976

J. Am. Chem. Soc.

102

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The 13C NMR spectra of the aconitine-type diterpenoid alkaloids aconitine, mesaconitine, deoxyaconitine, delphinine, chasmanine, delphisine, neoline, condelphine, isotalatizidine, as well as 17 related derivatives, have been obtained by the Fourier transform technique at 25.03 MHz. The signal due to each carbon atom has been assigned, and some previously published assignments in the alkamine, delphonine, and the alkaloid, isotalatizidine, are corrected. The spectra are analyzed in terms of substituent effects. On the basis of chemical correlation of chasmanine-neoline-delphisine, and similar values for the resonances in the 13C spectra of chasmanine, deoxyaconitine, delphinine, and delphonine, especially in the case of the ring A carbons, the configuration for the methoxyl at C-l in chasmanine has been revised to an «-equatorial methoxyl group. The results of a study of the "pyrodelphonine chromophore" in the electronic ground state of the molecule, using 13C and NMR techniques, are presented.

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Section: Introductionmentioning

confidence: 62%

Section: Discussion and Applicationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Carbon-13 nuclear magnetic resonance: aconitine-type diterpenoid alkaloids from Aconitum and Delphinium species

Pelletier¹,

Ďjarmati²

1976

J. Am. Chem. Soc.

102

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“…Wurde EtOH durch MeOH ersetzt, so bildete sich schon bei RT. 4 und 5 sowie eine dritte Substanz 6. In allen Fallen wurde auch, und zwar als grosster Anteil des Reaktionsgemisches Aconin (3) gefunden, dagegen niemals Benzoylaconin (2).…”

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Milde alkalische Hydrolyse von Aconitin

Katz¹,

Rudin²

1984

Helvetica Chimica Acta

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Mild Alkaline Hydrolysis of Aconitine SummaryHydrolysis of aconitine (1) with 0 . 0 4~ K,CO, in 90% MeOH at room temperature yields, besides the alkamine aconine 3 considerable amounts of 8-0 -methylaconine (6) and smaller quantities of desbenzoyl-pyroaconitine (4) and 16-epi-desbenzoyl-pyroaconitine (5). Better yields of 4 and 5 are obtained when heating a solution of aconitine in 0 . 0 4~ K,CO, in 90% EtOH. 7. Mitteilung iiber Aconitum. Mitteilung 6: [I]. Die Kristallisation von Benzoylaconin und die Beobachtung der Komplexitit der Hydrolyseprodukte wurde zuerst unter der Mitarbeit van Frl. Esther Stuehelin gemacht.

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“…In a normal method [11], firstly, we crushed the roots of A. hemsleyanum or A. geniculatum into powders. Secondly, above-mentioned powders (1.5 kg) were soaked by 10% sodium carbonate and extracted with chloroform.…”

Section: Separation Of Yunaconitine (1)mentioning

confidence: 99%

Partial Synthesis of Crassicauline A from Yunaconitine

Zhang

Lin

et al. 2020

Nat. Prod. Bioprospect.

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Both Aconitum hemsleyanum and Aconitum geniculatun have abundant contents of yunaconitine (1). Yunaconitine (1) has similar skeleton to crassicauline A (3); the only difference between them is that 1 contains a α-hydroxyl group at C-3. Our team attempts to convert 1 into 3 because 3 owns pharmacological activity. There are two steps to achieve the transformation above: firstly, use dehydration reaction to transform yunaconitine (1) into dehydroyunaconitine (2); secondly, use hydrogen reduction to acquire crassicauline A (3). Compared with other methods, this one below is more suitable for production application and more concise; moreover, the cost is lower with higher yield. Graphic AbstractKeywords Diterpenoid alkaloids · Yunaconitine · Crassicauline A

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Transformation of Aconitine to an Isomer of Hypaconitine

Cited by 9 publications

References 1 publication

Carbon-13 nuclear magnetic resonance: aconitine-type diterpenoid alkaloids from Aconitum and Delphinium species

Carbon-13 nuclear magnetic resonance: aconitine-type diterpenoid alkaloids from Aconitum and Delphinium species

Milde alkalische Hydrolyse von Aconitin

Partial Synthesis of Crassicauline A from Yunaconitine

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