Beiträge zur Chemie der Carbinolamine. I Untersuchungen an Py‐Tetrahydroisochinolinen

Schneider, Wilhelm; Müller, B.

doi:10.1002/jlac.19586150106

Cited by 33 publications

(8 citation statements)

References 15 publications

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“…The main quaternary alkaloid in P. pseudo-orientale was the well-known bicyclic isoquinoline cotarnine [5], here obtained as the iodide, C12H14N03I (27).…”

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confidence: 99%

Quaternary Isoquinoline Alkaloids from Papaver Species

Sarıyar¹,

Sarı²,

Guinaudeau³

et al. 1990

J. Nat. Prod.

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The two main quaternary alkaloids of Papaver cylindricum are the new phthalideisoquinoline (+ )-N-methyl-a-narcotine [1] and the known (-)-N-methylthebaine. Papaver pseudo-orientale provided (-)-a-N-methopapaverberbine [2], isolated as the iodide, which is the first N-methoprotoberberine salt hydroxylated at C-13, as well as the bicyclic cotarnine [5] and the quinoidal cotarnoline [7].Although several studies on the alkaloidal content of Papaver species (Papaveraceae) have been conducted in the past (1-3), only a limited number have actually focused on the quaternary alkaloids (4). We herewith report on the quaternary alkaloids in the aerial parts of two Turkish Papavers, namely Papaver cyclindricum Cullen and Papaver pseudo-orientale Fedde (Medw.).We have found that P. cylindricum has two main quaternary alkaloids. The first of these proved to be (+)-N-methyl-a-narcotine [1], which had never previously been isolated from a natural source. The existence of this salt had been conjectured, however, to explain the biogenesis of such secophthalideisoquinolines as narceine and nornarceine (5).(+)-N-Methyl-ct-narcotine [1] was isolated as the iodide salt, C23H26NO7I. The 'H-nmr spectrum in CDC13 has been summarized around structure 1. Two aromatic doublets sharing an 8.5 Hz coupling constant are readily assigned to H-2' ( 8.15) and H-3' ( 7.34). The H-5 aromatic singlet appears relatively upfield at 6.35. Three methoxyl singlets are in evidence at 3.91, 3 93, and 4.18 ppm, the last of which is due to the substituent at C-8. Finally, two N-methyl singlets are present, one at 3.45 and the other at 3.53 ppm. Of particular assistance in the spectral assignments was the presence of a long range benzylic coupling (0.8 Hz) between H-9 ( 6.23) and H-2'( 8.15), Because H-9 shows no other coupling, it is apparent that the dihedral angle it shares with H-l ( 6.36) approximates 90°. The present chemical shift assignments for (+ )-N-methyl-a-narcotine differ somewhat from those given more than ten years ago using a less sensitive nmr spectrometer (6).The mass spectrum of (+)-N-methyl-a-narcotine iodide indicated that Hofmann elimination followed by additional cleavages had occurred during the analytical process, because the base peak, m!z 58, is characteristic of the N, N-dimethy liminium cat-

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“…The main quaternary alkaloid in P. pseudo-orientale was the well-known bicyclic isoquinoline cotarnine [5], here obtained as the iodide, C12H14N03I (27).…”

mentioning

confidence: 99%

Quaternary Isoquinoline Alkaloids from Papaver Species

Sarıyar¹,

Sarı²,

Guinaudeau³

et al. 1990

J. Nat. Prod.

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“…Cactaceae: Backebergia militaris (41,46) Pachycereus weberi (5,6) Pilosocereus guerreronis (47) Nymphaeaceae: Nelumbo nucífera (48,49) Papaveraceae: Papaver bracteatum (23) Ranunculaceae: Thalictrum dioicum (43) Thalictrum polygamum (50) Synthetic (6,39,45,48,51) cuhbno2 191.0943 MP: 66°(52, 53) 61-61°( light petroleum ether) (10,22) (HC1) 263-269°(EtOH) (22) 274°( H20 (53) 276-278°(EtOH) (22) (Picrate) 175-176°(52) (Oxalate) 182-183° (39) (HBr) 293° (10) IR: (CC14) 2793 (54) (Nujol) (HC1) (D20) (22) T h i s c o n t e n t i s…”

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confidence: 99%

Simple Isoquinoline Alkaloids

Menachery¹,

Lavanier²,

Wetherly³

et al. 1986

J. Nat. Prod.

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“…Aus IR-spektroskopischen Untersuchungen lief3 sich der SchluB ziehen, daD die Struktur des kristallinen Cotarnins der Aminocarbinolform entspricht [12][13][14]. Obwohl die Aminoaldehydform auch in Losung nicht nachgewiesen werden kann15-19), 1aDt sich prinzipiell die Moglichkeit, daD sie in verschwindender Menge und in einer Konzentration unterhalb der Grenze der spektroskopischen Nachweisbarkeit dennoch anwesend ist und daf3 bei der Einwirkung gewisser Reagentien das Gleichgewicht in Richtung dieser Form verschoben wird, dennoch nicht ausschlieDen.…”

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Beiträge zur Chemie der heterocyclischen, pseudobasischen Aminocarbinole, XVI. Vergleichende kinetische Untersuchung der Reaktion des Cotarnins sowie einiger aromatischer Aldehyde mit Cyanwasserstoff

Beke

Szántay

Barczai-Beke

1960

Justus Liebigs Ann. Chem.

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Es wird der kinetische Verlauf der Reaktion des Cotarnins sowie einiger aromatischer Aldehyde (,,N-Methyl-cotarnin", m-Nitro-benzaldehyd) mit Cyanwasserstoff verglichen. Die wesentlichen Unterschiede in den kinetischen und thermodynamischen Parametern sowie in der Zuganglichkeit fur die Katalyse zwischen beiden Reaktionen schliel3en die Moglichkeit aus, dal3 das Cotarnin in seiner hypothetischen Aminoaldehydform an der Reaktion teilnimmt.Beziiglich der Struktur der aus heterocyclischen quartaren Ammoniumsalzen durch Alkalien freisetzbaren Basen hat sich allgemein die Anschauung verbreitet, da8 es sich bei diesen Verbindungen um Drei-Tautomeren-Systeme handele, bei welchen die quartare Ammoniumhydroxyd-, die pseudobasische Aminocarbinol-und die offenkettige Aminoaldehydform miteinander in einem mobilen Gleichgewicht stehen 1-71. Dementsprechend pflegt man das Cotarnin, einen typischen und zugleich den meistuntersuchten Vertreter dieser Verbindungsgruppe, als ein Gleichgewichtsgemisch der drei, den Strukturformeln I, IIa und IIIa entsprechenden Molekiilarten zu betrachten.

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Beiträge zur Chemie der Carbinolamine. I Untersuchungen an Py‐Tetrahydroisochinolinen

Cited by 33 publications

References 15 publications

Quaternary Isoquinoline Alkaloids from Papaver Species

Quaternary Isoquinoline Alkaloids from Papaver Species

Simple Isoquinoline Alkaloids

Beiträge zur Chemie der heterocyclischen, pseudobasischen Aminocarbinole, XVI. Vergleichende kinetische Untersuchung der Reaktion des Cotarnins sowie einiger aromatischer Aldehyde mit Cyanwasserstoff

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